JP2017019960A - Pressure-sensitive adhesive, pressure-sensitive adhesive film, and optical laminate using the same - Google Patents

Abstract

【Task】
A pressure-sensitive adhesive that has high peel strength, excellent optical properties and processability, and does not easily float or peel off when exposed to high-temperature or high-humidity environments. To provide a pressure-sensitive adhesive film.
[Solution]
An α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups in the molecule and an α, β-unsaturated double bond group-containing compound (a2) having no hydroxyl groups in the molecule A copolymer (A) obtained by polymerizing a monomer mixture and having a weight average molecular weight of 100,000 to 2,000,000 and a hydroxyl value of 0.1 to 50 mgKOH / g, and at least one P-OH A pressure-sensitive adhesive containing a compound or a compound (B) capable of forming one or more P-OH by hydrolysis, a silane compound (C) having an amino group or an epoxy group, and a polyisocyanate compound (D).
[Selection figure] None

Description

    The present invention relates to a pressure-sensitive adhesive that can be used for members such as plastic and glass.

    Display devices such as liquid crystal displays used in various devices such as home and commercial appliances such as electronic calculators, electronic watches, mobile phones, and televisions are becoming larger, especially liquid crystal televisions and plasma televisions. The increase in size is remarkable. In recent years, touch panel type liquid crystal displays such as smartphones and tablets are rapidly spreading, and a large market expansion is expected in the future. On the other hand, liquid crystal displays are also used in in-vehicle devices such as car navigation systems, and are required to have durability that can be used in harsh interior environments such as high-temperature and high-humidity atmospheres.

For such display devices, various films such as an antireflection film for preventing reflection from an external light source and a protective film (protection film) for preventing scratches on the surface of the display device are usually used. For example, in a liquid crystal cell member constituting an LCD, a polarizing film or a retardation film is laminated.
In addition to being used as a display device, a touch panel function may be provided on the surface to be used as an input device. A protective film, an antireflection film, an ITO vapor deposition resin film, or the like is also used for the touch panel.
Such a film is attached to an adherend via a pressure-sensitive adhesive and used in a display device. Since the pressure-sensitive adhesive used in the display device is required to have excellent transparency, a pressure-sensitive adhesive mainly composed of an acrylic resin is generally used.

  By the way, among the various films described above, the polarizing film generally has a three-layer structure in which both surfaces of a polyvinyl alcohol polarizer are sandwiched between triacetyl cellulose-based and cycloolefin-based protective films. For this reason, in a polarizing film, since the dimensional change characteristic of the material which comprises each layer differs, it is easy to produce the warp by the dimensional change accompanying the change of temperature or humidity.

On the other hand, for example, in an inspection process for a laminate in which a polarizing film is attached to a glass surface for a liquid crystal cell in an LCD manufacturing process, the polarizing film or the like is peeled off when there is air or dust entrainment during lamination. A new polarizing film or the like is reapplied. This re-pasting is also called “rework”.
However, since the laminated body after sticking is generally inspected after being stored at a high temperature for a certain period of time to improve adhesion, not only does the peel strength increase during that time, but it becomes difficult to peel off the polarizing film, After the releasability of the polarizing film was lowered and peeled off, contamination such as adhesive residue or cloudiness sometimes occurred on the glass surface.

In addition, since the polyvinyl alcohol film in the polarizing film undergoes a large dimensional change under high temperature or high temperature and high humidity conditions, for example, a laminate comprising a polarizing film / adhesive layer / glass is placed under high temperature or high temperature and high humidity conditions. If the dimensions of the polarizing film are changed, bubbles may be generated at the interface between the adhesive layer and the glass (foaming phenomenon), or the polarizing film may be lifted from the glass and peeled off (floating / peeling phenomenon).
Therefore, by adjusting the molecular weight of the pressure-sensitive adhesive and the degree of crosslinking of the pressure-sensitive adhesive and increasing the adhesive strength, the polarizing film does not foam, float, or peel even under harsh environments against dimensional changes. An attempt was made to do so.

  However, simply trying to resist the dimensional change of the polarizing film simply by increasing the adhesive force, the stress distribution due to the dimensional change of the polarizing film that occurs under high temperature or high temperature and high humidity conditions becomes non-uniform, and the stress is polarized. It concentrates on the four corners and the peripheral edge of the film. As a result, in the display device using the polarizing film, there is a problem that light leaks from the peripheral end portion of the display device, that is, so-called white spots occur.

On the other hand, various pressure-sensitive adhesives have been proposed.
For example, as a pressure-sensitive adhesive for a pressure-sensitive adhesive optical film, by adding a low molecular weight material such as a plasticizer to a resin copolymerized with an α, β-ethylenically unsaturated compound, a pressure-sensitive adhesive layer can be appropriately formed. A pressure-sensitive adhesive that is soft and imparts stress relaxation properties is disclosed (see, for example, Patent Document 1).

  In addition, for example, pressure-sensitive adhesives are known which are blended with resins obtained by copolymerizing α, β-ethylenically unsaturated compounds having different molecular weights and further contain a large amount of isocyanate group-containing crosslinking agents (for example, patents). Reference 2).

  Further, for example, in addition to a pressure-sensitive adhesive containing a resin copolymerized with an α, β-ethylenically unsaturated compound and a cross-linking agent, a material obtained by using a polyurethane resin in combination with a general resin is known. (See Patent Document 3).

However, an optical pressure-sensitive adhesive film using the pressure-sensitive adhesive described in Patent Documents 1 to 3 is exposed to a high temperature or a high temperature and high humidity condition for a long time after being attached to an adherend. In addition, a very small bubble composed of a resin obtained by copolymerizing a self-crosslinked product of an isocyanate group-containing crosslinking agent or a low molecular weight α, β-ethylenically unsaturated compound is formed in a streak shape at the peripheral edge of the optical film. Will occur. This phenomenon is called a “crack” because very small bubbles that appear as streaks look like a kind of crack.
In addition, about 10 bubbles of 10 μm or less, which cannot be confirmed unless using an electron microscope, are generated in the center part per 10 m ² .
Further, in a display device of 19 inches or more, the luminance of the light source must be set high from the viewpoint of easy viewing. The pressure-sensitive adhesive film for optical use (also referred to as optical adhesive film) formed by laminating and using the pressure-sensitive adhesive described in Patent Document 1 was not regarded as a problem in a display device of less than 19 inches. . However, there is also a problem that white spots are conspicuous in a display device using a high-intensity light source used at 19 inches or more due to cross-linking shrinkage due to a cross-linking agent and insufficient adhesion.

  In addition, for example, α, β-ethylenically unsaturated compounds containing aromatic rings are used as pressure-sensitive adhesives that do not cause appearance defects such as floating and peeling even under high-humidity and high-temperature environments by using the obtained copolymer. A copolymer resin obtained by copolymerizing a compound is disclosed (see Patent Document 4), and a copolymerization of an α, β-ethylenically unsaturated compound containing a heterocyclic ring is disclosed (patent). Reference 5). Further, a copolymer resin obtained by copolymerizing an α, β-ethylenically unsaturated compound having a carboxyl group and having a weight average molecular weight of 700,000 or more, and an α, β-ethylenically unsaturated compound having a weight average molecular weight of 800 to 50,000. A technique for improving the stress relaxation property by using together with a copolymer resin obtained by copolymerizing a polymer is disclosed (see Patent Document 6).

  However, the copolymer resin obtained by copolymerizing an α, β-ethylenically unsaturated compound containing an aromatic ring or a heterocycle disclosed herein has an extremely high solution viscosity, and has an optical sensitivity. When producing a pressure-type adhesive film (optical adhesive film), it is difficult to produce it unless the non-volatile content is reduced as much as possible, and there are many problems in terms of coating processability and cost from an industrial viewpoint. Further, the obtained pressure-sensitive adhesive film for optical use (optical adhesive film) does not cause floating or peeling under a heat aging environment of 80 ° C. or 60 ° C.-90% relative humidity, but it is a more severe environment. For example, in an environment of 100 ° C. heat aging or 85 ° C.-relative humidity 90% wet heat aging, the durability is not sufficient, the cohesive force is significantly reduced, and cracks and foaming are likely to occur. It was.

  On the other hand, in order to impart removability (sometimes referred to as reworkability), the acid value is high and the weight average molecular weight is 0.2 to 10 for a high molecular weight acrylic polymer having a weight average molecular weight of 500,000 or more. A technique for blending 10,000 low molecular weight acrylic polymers is disclosed (see Patent Document 7).

  Furthermore, a technique for improving the stress relaxation property by using together an acrylic polymer having a carboxyl group and a weight average molecular weight of 700,000 or more and an acrylic polymer having a weight average molecular weight of 800 to 50,000 is disclosed. (See Patent Document 8).

  In addition, a technique for improving durability and adhesive properties under heating and humidification conditions by using a block polymer using two or more kinds of monomers is disclosed (see Patent Document 9).

  Further, by a water-dispersed pressure-sensitive adhesive containing an acrylic copolymer having a glass transition temperature of −55 ° C. or higher and lower than 0 ° C. and an acrylic copolymer having a glass transition temperature of 0 ° C. or higher and 180 ° C. or lower, A technique that hardly causes depolarization and imparts reworkability and recyclability has been disclosed (see Patent Document 10).

  Further, a technique for improving a good adhesive force is disclosed by a water-dispersed pressure-sensitive adhesive mainly composed of an acrylic copolymer copolymerized with a monomer having a phosphonyl group and containing a phosphate ester compound ( (See Patent Document 11).

  However, the pressure-sensitive adhesive described in Patent Document 7 has a problem that the drying conditions of the pressure-sensitive adhesive are limited. Further, the pressure-sensitive adhesive described in Patent Document 8 has a problem that the cohesive force is remarkably reduced, and the pressure-sensitive adhesive described in Patent Document 9 has a problem that the transmittance under heating and humidification conditions is decreased. In addition, the pressure-sensitive adhesives described in Patent Documents 10 and 11 have a problem of contaminating an adherend such as glass due to the influence of various additives used in the pressure-sensitive adhesive and the hygroscopicity associated therewith. .

  Furthermore, as a crosslinking agent to be used, an adhesive containing a polyacrylic resin and an epoxy resin is disclosed (see Patent Document 12). Further, an adhesive using a polyacrylic resin and ethyleneimine is disclosed (see Patent Document 13). Furthermore, an adhesive using a polyacrylic resin having a carboxyl group, a hydroxyl group, and a glycidyl group is disclosed (see Patent Document 14). Moreover, the adhesive agent with which the carboxyl group containing macropolyol and the carbodiimide group containing compound were mix | blended is disclosed (refer patent document 15).

  However, in Patent Document 12, in the polyacrylic resin and the epoxy resin, the functional group capable of crosslinking reaction with the glycidyl group is not incorporated in the polyacrylic resin, the crosslinking reactivity of the glycidyl group is poor, and the epoxy resin remains. There are concerns. When the remaining epoxy resin is hydrolyzed, two hydroxyl groups are generated, and the heat and moisture resistance and water resistance may be lowered. Moreover, in patent document 13, since the water solubility of ethyleneimine is high, the heat-and-moisture resistance and the water resistance fall, or the storage stability of ethyleneimine is bad, it may cause adhesion failure. Furthermore, in Patent Document 14, two or more types of functional groups capable of crosslinking reaction are copolymerized in the polyacrylic resin, and the pot life (also referred to as pot life) and storage stability are improved by the self-crosslinking reaction. May decrease. Patent Document 15 is a system utilizing the reaction between a carboxyl group and a carbodiimide group, but the crosslinking reactivity between the carboxyl group and the carbodiimide group is high, and the storage stability may deteriorate, and the carbodiimide group-containing compound If the amount is reduced, the cohesive force after the cross-linking reaction may be insufficient, and it may not be possible to secure a balance of adhesive strength.

In view of such a situation, while maintaining high heat resistance and high heat-and-moisture resistance, a decrease in pressure-sensitive adhesive properties and optical properties is suppressed, and it can be used from film label applications to electrical and optical applications. A highly sensitive pressure sensitive adhesive has been desired.
Furthermore, a pressure-sensitive adhesive having both transparency, solubility in resin and solvent (compatibility), and heat-and-moisture resistance has been desired.

Japanese Patent Laid-Open No. 9-87593 JP 2001-049200 A JP 2003-073646 A JP 2003-193012 A JP 2007-277510 A JP 2004-069975 A JP 2010-1000071 A JP 2004-069975 A Japanese Patent Application Laid-Open No. 2013-082772 JP 2014-001365 A JP 2008-266506 A Japanese Examined Patent Publication No.59-037034 JP 05-287250 A Japanese Patent No. 3660477 JP 2010-159339 A

  The problem to be solved by the present invention is to solve the above-mentioned problems, when used in a pressure-sensitive adhesive film, having high peel strength, excellent optical characteristics and workability, in a high-temperature environment or at high temperature and high humidity. An object of the present invention is to provide a pressure-sensitive adhesive that hardly causes lifting or peeling from a substrate even when exposed to an environment, and a pressure-sensitive adhesive film using the pressure-sensitive adhesive. In addition, when used for polarizing plates, light leakage is unlikely to occur, removability is good, and even when exposed to high-temperature and high-humidity environments, it maintains high transparency that is unlikely to lift or peel off from the substrate. An object of the present invention is to provide a pressure-sensitive adhesive and a pressure-sensitive adhesive film using the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned goal can be achieved by the pressure-sensitive adhesive shown below, and have completed the present invention.

  That is, the present invention includes an α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups in the molecule and an α, β-unsaturated double bond group having no hydroxyl groups in the molecule. A copolymer (A) obtained by polymerizing a monomer mixture containing the compound (a2) and having a weight average molecular weight of 100,000 to 2,000,000 and a hydroxyl value of 0.1 to 50 mgKOH / g; Contains a compound having one or more OH or a compound (B) capable of forming one or more P-OH by hydrolysis, a silane compound (C) having an amino group or an epoxy group, and a polyisocyanate compound (D) It relates to a pressure sensitive adhesive.

    In addition, the present invention provides a compound having one or more P—OH or a compound (B) capable of forming one or more P—OH by hydrolysis with respect to 100 parts by weight of the copolymer (A). 10 to 10 parts by weight, 0.01 to 10 parts by weight of a silane compound (C) having an amino group or an epoxy group, and 0.1 to 30 parts by weight of a polyisocyanate compound (D) It relates to a pressure-sensitive adhesive.

    The present invention also relates to the pressure-sensitive adhesive, wherein the compound having one or more P-OH or the compound (B) capable of forming one or more P-OH by hydrolysis is phosphoric acid (b1).

    Moreover, this invention relates to the said pressure sensitive adhesive which contains the silane compound (E) which does not have an amino group and an epoxy group further.

    Moreover, this invention relates to the pressure sensitive adhesive film formed by laminating | stacking the contact bonding layer containing the said pressure sensitive adhesive on the at least one surface of a base material (G).

    Moreover, this invention relates to the said pressure sensitive adhesive film whose base material (G) is a transparent film (H).

    Moreover, this invention relates to the said pressure sensitive adhesive film whose transparent film (H) is optical film (I).

    The present invention also relates to an optical laminate in which the optical film (I), an adhesive layer formed from the pressure-sensitive adhesive, and glass are sequentially laminated.

  According to the present invention, it can be suitably used for adhesion of an optical member that can form a pressure-sensitive adhesive film excellent in adhesion to a substrate, removability (reworkability), heat resistance, moist heat resistance and transparency. Possible pressure sensitive adhesives have been provided. In addition, foaming or peeling from the substrate is unlikely to occur even at high temperatures or high humidity, reducing stress concentration caused by expansion and contraction of optical films such as polarizing films, etc. It has become possible to provide an optical laminate that does not occur.

Hereinafter, embodiments of the present invention will be described.
The pressure-sensitive adhesive of the present invention comprises an α, β-unsaturated double bond group-containing compound (a1) containing one or more hydroxyl groups in the molecule and an α, β-unsaturated diester containing no hydroxyl group in the molecule. A copolymer (A) obtained by polymerizing a monomer mixture containing the heavy bond group-containing compound (a2) and having a weight average molecular weight of 100,000 to 2,000,000 and a hydroxyl value of 0.1 to 50 mgKOH / g. And phosphoric acid or a derivative thereof (B), a silane compound (C) having an amino group or an epoxy group, and a polyisocyanate compound (D).
In this specification, “(meth) acryl”, “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, and “(meth) allyl” Unless otherwise specified, “acrylic or methacrylic”, “acryloyl or methacryloyl”, “acrylic acid or methacrylic acid”, “acrylate or methacrylate”, “acryloyloxy or methacryloyloxy”, And “allyl or methallyl”.

Hereinafter, the components of the pressure-sensitive adhesive will be specifically described.
<Copolymer (A)>
The copolymer (A) comprises an α, β-unsaturated double bond group-containing compound (a1) containing one or more hydroxyl groups in the molecule and an α, β-unsaturated double containing no hydroxyl group in the molecule. It is a resin obtained by polymerizing a monomer mixture containing the binding group-containing compound (a2). The α, β-unsaturated double bond group-containing compound (a1) containing one or more hydroxyl groups in the molecule includes one or more hydroxyl groups and one or more α, β-unsaturated compounds in the structure. A compound containing a saturated double bond group. As such a compound (a1), the compound (a1-1) having a hydroxyl group in the molecule and having no cyclic structure and a hydroxyl group in the molecule, It can be classified into the compound (a1-2) having a cyclic structure. Specific examples include the following compounds.

  Of the α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups in the molecule, the compound (a1-1) having a hydroxyl group and not having a cyclic structure is Is a compound having a hydroxyl group but having a cyclic structure, such as 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic. 3-hydroxypropyl acid, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic 6-hydroxyhexyl acid, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylic acid Ester, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), monofunctional (meth) acrylate glycerol, or (meth) acryl Fatty acid ester-based (meth) acrylic acid ester such as glycidyl lauric acid ester, glycidyl oleic acid (meth) acrylate, glycidyl stearate (meth) acrylate, or 2- (acryloyloxy) ethyl 6-hydroxyhexa (Meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound such as nonate, and the hydroxyl group-containing α , Β-ethylenically unsaturated double bond group Ethylene oxide relative to compound, propylene oxide, alkylene oxide adduct (meth) aliphatic hydroxyl group-containing acrylic acid ester obtained by repeatedly adding an alkylene oxide such as butylene oxide (meth) acrylate;

  For example, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, triethylene glycol Hydroxyl-containing aliphatic vinyl ethers such as methylolpropane monovinyl ether, pentaerythritol monovinyl ether, or alkylene oxide-added vinyl ether having a hydroxyl group at the terminal where alkylene oxide such as ethylene oxide or propylene oxide is repeatedly added;

  For example, (meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether , Hydroxyoctyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether, or alkylene oxides such as ethylene oxide and propylene oxide Hydroxyl group-containing aliphatic (meth) allyl alcohols such as alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the terminal of repeating addition of Or (meth) allyl ethers;

  For example, α, β-unsaturated double bond group-containing compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, and glycerol di (meth) acrylate;

  For example, hydroxyl groups such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide, etc. Of (meth) acrylamides;

  Examples thereof include monomers having a hydroxyl group and a vinyl group such as vinyl alcohol, but are not particularly limited thereto. These may use only 1 type or may use multiple types together. As the compound (a1-1), from the viewpoint of adhesion to the substrate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ε -Caprolactone 1-2 mol addition (meth) acrylic acid 2-hydroxyethyl etc., C2-C18 alpha, beta-unsaturated double bond group containing compound is especially preferable.

  Among the α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups in the molecule, the compound (a1-2) having a hydroxyl group and having a cyclic structure is included in the structure. If it has both a hydroxyl group and a cyclic structure, there will be no restriction | limiting in particular, For example, (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (meth) acrylate, 2-hydroxy-3-phenoxymethyl (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, 2-hydroxy- (meth) acrylate 3-phenoxypropyl, 2-hydroxy-3-phenoxybutyl (meth) acrylate, 2-hydroxy-3-phenoxy (meth) acrylate Hydroxyl groups and hydrocarbons such as decyl, (meth) acrylic acid 2-hydroxy-3-phenoxyoctadecyl, (meth) acrylic acid monohydroxyethyl phthalate, (meth) acrylic acid 2- (4-benzoyl-3-hydroxyphenoxy) ethyl (Meth) acrylic acid esters having a ring;

  For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- Hydroxyl group-containing benzophenone-based (meth) acrylic esters such as (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

  For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole; 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, and 2- (2'-hydroxy -3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-ben Hydroxyl group-containing benzotriazole-based triazole (meth) acrylic acid esters;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy }]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy-4- {2- Meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S- Hydroxyl-containing triazines such as triazine and 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine (meta ) Acrylic acid esters and the like, and these may be used alone or in combination of two or more.

  As the compound (a1-2), (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedi, in terms of durability such as heat resistance, moist heat resistance, and water resistance. Methanol, (meth) acrylic acid 1,4-cyclohexanedimethanol, (meth) acrylic acid 2-hydroxy-3-phenoxypropyl and the like are particularly preferable.

Thus, by copolymerizing the compound (a1), a preferable polymerization rate is obtained, and it becomes easy to control the molecular weight and the crosslinking density of the copolymer (A). Accordingly, when the copolymer (A) is used as a pressure-sensitive adhesive, it is possible to form a crosslinked coating film having high cohesive strength. Moreover, the compound (B) which can form one or more P-OH by hydrolysis, the compound (B) which has one or more P-OH mentioned later, the silane compound (C) which has an amino group, or an epoxy group, and a polyisocyanate compound ( D) is improved in cross-linking reactivity and can be expected to improve cohesion, so when producing an optical laminate used for an optical member, not only is it excellent in heat resistance, moist heat resistance, water resistance, etc., but sufficient It becomes easy to impart processability.

In the copolymer (A), the α, β-unsaturated double bond group-containing compound (a2) that does not have a hydroxyl group in the molecule and constitutes the copolymer (A) will be described.
The compound (a2) is a compound containing an α, β-unsaturated double bond group that does not have a hydroxyl group in the molecule, and the component (a2) is contained in the copolymer (A), thereby It is easy to increase the efficiency of the copolymerization reaction with the compound (a1). In addition, the viscosity of the copolymer (A) can be easily reduced, and the workability during coating can be easily improved. In addition, the glass transition temperature (hereinafter referred to as Tg) of the coated product is controlled to improve adhesiveness (also referred to as tack), and the cohesive force of the coating film is improved to improve heat resistance and water resistance. It is possible to form a good pressure-sensitive adhesive layer. The α, β-unsaturated double bond group-containing compound (a2-1) is preferably a homopolymer (also referred to as a homopolymer) having a Tg of 0 ° C. or lower and an alkyl group in the side chain. By copolymerizing the compound (a2-1), it is possible to impart tack to the copolymer (A), and it can be usefully used as a pressure-sensitive adhesive.

Here, the glass transition temperature (Tg) is measured using a differential scanning calorimeter (DSC) described later, but can be theoretically calculated by the following FOX equation.
<FOX type> 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wi / Tgi + ... + Wn / Tgn
[In the above FOX formula, the glass transition temperature of a homopolymer of each compound constituting a polymer comprising n kinds of α, β-unsaturated double bond group-containing compounds is Tgi (K), and the mass fraction of each compound The rate is Wi, (W1 + W2 + ... + Wi + ... Wn = 1). ]

  Furthermore, the value described in literature can be used for Tg of a homopolymer. As such documents, for example, the following documents can be referred to: Mitsubishi Rayon Co., Ltd. acrylic ester catalog (2001 edition); Osaka Organic Chemical Industry Co., Ltd. catalog (2009 edition); Hitachi Chemical Co., Ltd. funkrill catalog ( 2007 edition); and "POLYMER HANDBOOK" 3rd edition, pages 209-277, John Wiley & Sons, Inc. 1989. In addition, Tg of the copolymer (A) in this specification is determined using the below-mentioned differential scanning calorimeter (DSC).

  Among the compounds (a2), the α, β-unsaturated double bond group-containing compound (a2-1) having a homopolymer Tg of 0 ° C. or lower and an alkyl group includes, for example, ethyl acrylate, acrylic N-propyl acid, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, pentyl acrylate, isoamyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) Octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3,4-dimethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, (meth) acryl 3,4-dimethylheptyl acid, decyl (meth) acrylate, lauryl (meth) acrylate, a Examples include (meth) acrylic acid alkyl esters such as isostearyl crylate, and among these, n-butyl acrylate and 2-ethylhexyl acrylate are preferable from the viewpoint of easily developing good tack. These may be used alone or in combination of two or more.

  Of the compound (a2), the homopolymer has a Tg of 0 ° C. or lower and contains an α, β-unsaturated double bond group other than the α, β-ethylenically unsaturated compound (a2-1) having an alkyl group As the compound (a2-2), other than the compound (a2-1), as appropriate, based on the viscosity, durability, optical characteristics, coating suitability, etc. of the pressure-sensitive adhesive formed from the copolymer (A) It is possible to select an α, β-unsaturated double bond group-containing compound. However, the compound (a1) is not included. More specific examples of such α, β-unsaturated double bond group-containing compound (a2-2) include, for example, methyl (meth) acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate. , N-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl (meth) acrylate, pentyl methacrylate, isoamyl methacrylate, stearyl (meth) acrylate, and the like. (Meth) acrylic acid alkyl esters exceeding ℃;

  For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-butenyl, (meth) acrylic acid 2-chloro-2-propenyl, (meth) acrylic acid 3-chloro-2-propenyl, (meth) acrylic acid 2- (2-propenyloxy) ethyl, (meth) acrylic acid 2- Propenyl lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7-dimethyloct-2,6-dien-1-yl, (Meth) acrylic acid esters further containing an unsaturated group such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate;

  For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic propenoic acid 2-perf Orodeshiruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

  For example, fluorine-containing vinyl compounds such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;

  For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate Alkoxy group-containing (meth) acrylic acid esters such as ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate;

  For example, (meth) acrylic acid-containing (meth) acrylic acid derivatives having an alkylene oxide adduct such as ethylene oxide and propylene oxide and having no hydroxyl group at the end;

  For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , (Meth) acrylic acid 2- (ethoxyca (Rubonyloxy) butyl, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, (meth) 2- (Butoxycarbonyloxy) ethyl acrylate, 2- (butoxycarbonyloxy) butyl (meth) acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, 2- (octyloxy) (meth) acrylate Aliphatic (meth) acrylic acid esters having one carbonyl group such as carbonyloxy) butyl;

  For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (Meth) acrylic acid 2-oxobutanoyloctyl, (meth) acrylic acid 2-oxobutanoyldecyl, (meth) acrylic acid 2-oxobutanoyldodecyl, (meth) acrylic acid 3-oxobutanoylethyl, ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylate (Meth) acrylic acid 4-cyanooxobutanoylethyl, (meth) acrylic acid 4-cyanooxobutanoylpropyl, (meth) acrylic acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoyl Ruhexyl, 4-cyanooxobutanoyloctyl (meth) acrylate, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, ( Aliphatic (meth) acrylic acid esters having two carbonyl groups such as 2,3-di (oxobutanoyl) hexyl (meth) acrylate and 2,3-di (oxobutanoyl) octyl (meth) acrylate Kind;

For example, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl, (meth) acrylic acid-10-methoxycarbonyl -5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] non-2-yl, (meth) acrylic acid-4-methoxycarbonyl-6-oxo-7-oxa-bicyclo [3 2.1] having a carbonyl group such as octa-2-yl, (meth) acrylic acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl ( (Meth) acrylic acid cyclic esters;

  For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecane Vinyl acetate, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyroyl acetate , Vinyl propanoyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, palmitoyl vinyl valerate, stearoyl valerate, pyrvoyl Vinyl ester compounds such aliphatic having Rerin acid acyl group vinyl, and the like;

  For example, aliphatic vinyl ether compounds having an acyl group such as 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxybutyl vinyl ether, 2-acetoacetoxyhexyl vinyl ether, 2-acetoacetoxyoctyl vinyl ether;

  For example, vinyl esters of aliphatic carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, vinyl palmitate, vinyl stearate;

  For example, aliphatic such as (meth) allyl acetate, (meth) allyl propionate, (meth) allyl butyrate (meth) allyl caprate, (meth) allyl laurate, allyl octylate, coconut oil fatty acid, vinyl pivalate, etc. (Meth) allyl esters of carboxylic acids;

  For example, vinyl halides such as vinyl chloride, vinylidene chloride and allyl chloride;

  For example, methyl vinyl ether, ethyl vinyl ether, 2-chlorovinyl ether, n-propyl vinyl ether, allyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, tert -Pentyl vinyl ether, n-hexyl vinyl ether, isohexyl vinyl ether, 2-ethylbutyl vinyl ether, 2-ethylhexyl vinyl ether, n-heptyl vinyl ether, n-octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, hexanedecyl vinyl ether , Octa Sil vinyl ether, ethoxymethyl vinyl ether, 2-methoxyethyl vinyl ether, 2-ethoxyethyl vinyl ether, 2-butoxyethyl vinyl ether, acetoxymethyl vinyl ether, 2-acetoxyethyl vinyl ether, 3-acetoxypropyl vinyl ether, 4-acetoxybutyl vinyl ether, 4-ethoxy Butyl vinyl ether, 2- (2-methoxyethoxy) ethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, diethylene glycol methyl vinyl ether, diethylene glycol ethyl vinyl ether, diethylene glycol butyl vinyl ether, etc. The aliphatic Vinyl ether compounds;

  For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether (DEGVE), triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol Divinyl ether, butanediol divinyl ether, neopentyl glycol divinyl ether, hexanediol divinyl ether, nonanediol divinyl ether, hydroquinone divinyl ether, 1,4-cyclohexanediol divinyl ether (CHODVE), 1,4-cyclohexanedimethanol divinyl ether ( HDVE), trimethylolpropane trivinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether (TMPEOTVE), pentaerythritol tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ditrimethylolpropane tetravinyl ether, dipentaerythritol hexavinyl ether, etc. Vinyl ethers;

  For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyldipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrime Kishishiran, 3- (meth) acryloyloxy propyl triethoxysilane, 3- (meth) acryloyl alkoxysilyl group-containing (meth) acrylic acid esters such as propyl tripropoxysilane;

  For example, alkoxysilyl such as (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxyvinylsilane, vinyltris (2-methoxyethoxy) silane Group-containing α, β-ethylenically unsaturated compounds;

  For example, halogen-containing silyl group-containing (meth) allyl compounds such as (meth) allylchlorosilane and (meth) allylbromosilane;

  For example, di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid polyethylene oxide, di (meth) acrylic acid propylene oxide, di (Meth) acrylic acid dipropylene oxide, di (meth) acrylic acid tripropylene oxide, di (meth) acrylic acid polypropylene oxide, di (meth) acrylic acid butene oxide, di (meth) acrylic acid pentane oxide, di (meth) 2,2-dimethylpropyl acrylate, hydroxypivalylhydroxypivalate di (meth) acrylate, hydroxypivalylhydroxypivalate hydroxypivalate dicaprolactonate, 1,6-hexane di (meth) acrylate Gio Di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7- Heptanediol, 1,8-octanediol di (meth) acrylic acid, 1,2-octanediol di (meth) acrylic acid, 1,9-nonanediol di (meth) acrylic acid, 1, di (meth) acrylic acid 1, 2-decanediol, di (meth) acrylic acid 1,10-decanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodecanediol, di (meth) acrylic acid 1,2-dodecanediol, di (meth) acrylic acid 1,14-tetradecanediol, di (meth) acrylic acid 1,2-tetradecanediol, di (meth) a 1,16-hexadecanediol silylate, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentanediol di (meth) acrylate, 3-methyl-1 di (meth) acrylate , 5-pentanediol, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, di (meth) 2,2-diethyl-1,3-propanediol acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, di (meth) 2-ethyl-1,3-hexanediol acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-methyl di (meth) acrylate , 8-octanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, di (meth) 2-methyl-2-propyl-1,3-propanediol acrylate, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1, di (meth) acrylate 3-propanediol, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-di (meth) acrylate Hexanediol, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, di (meth) acrylate ) Bifunctional (meth) acrylic acid esters such as 2,4-diethyl-1,5-pentanediol acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate;

  For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate Tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, Trifunctional (meth) acrylic esters such as pentaerythritol tri (meth) acrylate;

  For example, tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid ethoxylated pentaerythritol, tetra (meth) acrylic acid ditrimethylolpropane, hexa (meth) acrylic acid dipentaerythritol, tetra (meth) acrylic acid 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1, 2,3-propanetriol, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, tetra ( (Meth) acrylic acid di-2,2-dimethylpropane-1,3- All, tetra (meth) acrylate ditrimethylolbutane, tetra (meth) acrylate ditrimethylolhexane, tetra (meth) acrylate ditrimethyloloctane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1, 3-propanediol, hexa (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol , Hepta (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meta ) Di2,2-bis (hydroxymethyl) 1,3-propanediol acrylate Polyfunctional (meth) acrylic acid esters or tetrafunctional such real sharp emission oxide;

  For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Α, β-ethylenically unsaturated compounds containing polyfunctional unsaturated bonds such as vinyl 12,15-trienoate;

For example, cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, (meth ) 1-methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate Benzyl (meth) acrylate, iso-bornyl (meth) acrylate, phenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-oxo-1,2-phenylethyl (meth) acrylate, (Meth) acrylic acid 2-oxo-1,2-diphenylethyl, (meth) acrylic acid 1 Naphthyl, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, (meth ) 9-anthrylmethyl acrylate, 2-methyladamantyl-2-yl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate Oxyethyl, 2-ethyladamantyl-2-yl (meth) acrylate, 2-n-propyladamantyl-2-yl (meth) acrylate, 2-isopropyladamantyl-2-yl (meth) acrylate, (meth) 1- (adamantan-1-yl) -1-methylethyl acrylate, 1- (ada) (meth) acrylic acid Ntan-1-yl) -1-ethylethyl, 1- (adamantan-1-yl) -1-methylpropyl (meth) acrylate, 1- (adamantan-1-yl) -1-ethylpropyl (meth) acrylate , (Meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [ 5.2.1.0 ^3,8 ] dec-2-yl, dihydro-α-terpinyl (meth) acrylate, (meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] Oct-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (Meth) acrylic acid-o-2-prope (Meth) acrylic acid alicyclic esters such as nylphenyl;

  For example, vinyl benzoylformate, vinyl benzoyl acetate, vinyl benzoylpropionate, vinyl benzoylbutyrate, vinyl benzoylvalerate, vinyl benzoylhexanoate, vinyl benzoyldodecanoate, 1-naphthoylvinyl acetate, 1-naphthoylpropionate, 1- Naphthoyl vinyl butyrate, 1-naphthoyl vinyl valerate, 1-naphtho vinyl hexanoate, 2-naphtho vinyl acetate, 2-naphtho vinyl propionate, 2-naphtho vinyl butyrate, 2-naphtho vinyl butyrate, 2- Vinyl naphthoyl hexanoate, vinyl nicotinoyl acetate, vinyl nicotinoyl propionate, vinyl nicotinoyl butyrate, vinyl nicotinoyl valerate, vinyl nicotinoyl hexanoate, vinyl nicotinoyl decanoate, nicotine Vinyl dodecanoate, vinyl isonicotinoyl acetate, vinyl isonicotinoyl propionate, vinyl isonicotinoyl butyrate, vinyl isonicotinoyl valerate, vinyl isonicotinoyl hexanoate, vinyl isonicotinoyl decanoate, vinyl isonicotinoyl dodecanoate, 2-furoyl Vinyl acetate, vinyl 2-furoylpropionate, vinyl 2-furoylbutyrate, vinyl 2-furoylvalerate, vinyl 2-furoylhexanoate, vinyl 2-furoyldecanoate, vinyl 2-furoyldodecanoate, 3-furoyl Vinyl acetate, vinyl 3-furoylpropionate, vinyl 3-furoylbutyrate, vinyl 3-furoylvalerate, vinyl 3-furoylhexanoate, vinyl 3-furoyldecanoate, vinyl 3-furoyldodecanoate, vinyl anthraniloyl acetate , Aromatic carboxylic acids having an acyl group such as vinyl anthraniloyl propionate, vinyl anthraniloyl butyrate, vinyl anthraniloyl valerate, vinyl anthraniloyl hexanoate, vinyl anthraniloyl decanoate, vinyl anthraniloyl decanoate, etc. Vinyl ester compounds of

  For example, acetoacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovaleric acid (meth) allyl, acetohexanoic acid (meth) allyl, aceto-2- Ethylhexanoic acid (meth) allyl, aceto-n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, Stearoyl acetate (meth) allyl, (meth) allyl Aliphatic (meth) allyl compounds having an acyl group such as hydrin;

  For example, benzoyl formate (meth) allyl, benzoyl acetate (meth) allyl, benzoylpropionate (meth) allyl, benzoylbutyrate (meth) allyl, benzoylvalerate (meth) allyl, benzoylhexanoic acid (meth) allyl, benzoyldodecanoic acid (Meth) allyl, 1-naphthoylacetic acid (meth) allyl, 1-naphthoylpropionic acid (meth) allyl, 1-naphthoylbutyric acid (meth) allyl, 1-naphthoylvaleric acid (meth) allyl, 1-naphthoylhexane Acid (meth) allyl, 2-naphthoylacetic acid (meth) allyl, 2-naphthoylpropionic acid (meth) allyl, 2-naphthoylbutyric acid (meth) allyl, 2-naphthoylvaleric acid (meth) allyl, 2-naphthoyl Aromatic (meth) allyl having an acyl group such as hexanoic acid (meth) allyl Compound class;

  For example, di (meth) acrylic acid tricyclodecane dihydroxymethyl, di (meth) acrylic acid tricyclodecane dihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantanediol, di (meth) acrylic acid 1 , 3-adamantanediol, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, di (meth) acrylate di Cyclopentenyl, dicyclopentenyloxyethyl di (meth) acrylate, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2-hydroxypropyl) di (meth) acrylate ) Benzene, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propyl Tetraethylene oxide adduct of bread, tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) methane di (meth) acrylate, tetraethylene oxide of di (meth) acrylic acid-4,4′-sulfonyldiphenol Adduct, Di (meth) acrylic acid-hydrogenated 2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct, Di (meth) acrylic acid-hydrogenated 2,2-bis (hydroxyphenyl) methane tetra Ethylene oxide adduct, di (meth) acrylic acid-hydrogenated 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-hydrogenated 2,2-bis (hydroxyphenyl) methane, di (meta ) Tetraethylene oxide adduct of acrylic acid-2,2-bis (hydroxyphenyl) propane- Bifunctional (meth) acrylic acid cyclic esters such as dicaprolactonate, tetraethylene oxide adduct of di (meth) acrylic acid-2,2-bis (hydroxyphenyl) methane-dicaprolactonate;

  For example, 5-vinylbicyclo [2.2.1] hept-2-ene, 2,5-bis (allyloxy) norbornane, 5-vinyl-2,3-oxirane norbornane, 2- (2-propenyl) bicyclo [2 2.1] heptane, 5-vinylbicyclo [2.2.1] hept-2-ene, 2-ethenylideneadamantane, 1-allyladamantane, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, cyclohexyl ethyl vinyl ether, menthyl vinyl ether, Alicyclic vinyl ethers such as tetrahydrofurfuryl vinyl ether, norbornenyl vinyl ether, 1-adamantyl vinyl ether, 2-adamantyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, 1-naphthyl vinyl ether, 2-naphthyl vinyl ether Tells;

  For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t- Butoxy-α-methylstyrene, 4- (2-ethyl-2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- ( 1-ethoxyethoxy) -α-methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene, 4- (2-t-ethoxycarbonylethyloxy) styrene, 4- (2-t-butoxycarbonylethyl) Oxy) styrene, 4- (2-t-butoxycarbonylpropyloxy) styrene and other styrene-based aromatic vinyl Le-based compounds;

  For example, vinyl phenyl pentyl ether, vinyl phenyl hexyl ether, vinyl phenyl heptyl ether, vinyl phenyl octyl ether, vinyl phenyl nonyl ether, vinyl phenyl decyl ether, vinyl phenyl undecyl ether, vinyl phenyl dodecyl ether, vinyl phenyl tridecyl ether, vinyl Phenyl tetradecyl ether, vinyl phenyl pentadecyl ether, vinyl phenyl hexadecyl ether, vinyl phenyl heptadecyl ether, vinyl phenyl octadecyl ether, vinyl phenyl nonadecyl ether, vinyl phenyl eicosyl ether, vinyl phenyl henecosyl ether, vinyl phenyl doco Sil ether, vinyl phenyl methyl butyl ether, vinyl phenyl Rupentyl ether, vinyl phenyl methyl hexyl ether, vinyl phenyl methyl heptyl ether, vinyl phenyl methyl octyl ether, vinyl phenyl methyl nonyl ether, vinyl phenyl methyl decyl ether, vinyl phenyl methyl undecyl ether, vinyl phenyl methyl dodecyl ether, vinyl phenyl methyl Tridecyl ether, vinyl phenylmethyl tetradecyl ether, vinyl phenyl methyl pentadecyl ether, vinyl phenyl methyl hexadecyl ether, vinyl phenyl methyl heptadecyl ether, vinyl phenyl methyl octadecyl ether, vinyl phenyl methyl nonadecyl ether, vinyl phenyl methyl eicosyl Ether, vinyl phenyl methyl henecosyl ether, vinyl Aromatic vinyl phenyl ether compounds having a long chain alkyl group, such as E methylpropenylmethyl docosyl ether;

  For example, hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate , Octadecyl 4-vinylbenzoate, eicosyl 4-vinylbenzoate, docosyl 4-vinylbenzoate, hexyl 4-isopropenylbenzoate, octyl 4-isopropenylbenzoate, nonyl 4-isopropenylbenzoate, 4-isopropenyl Decyl benzoate, 4-isopropenylbenzoic acid dodecyl, 4-isopropenylbenzoic acid tetradecyl, 4-isopropenylbenzoic acid hexadecyl, 4-isopropenylbenzoic acid octadecyl, 4-isopropenylbenzoic acid eicosyl, 4-isopropenylbenzoic acid Docosil How long chain vinyl benzoic acid ester or isopropenyl benzoic acid ester compounds having an alkyl group;

  For example, tetra (ethylene oxide) vinyl phenyl ether, methyl tetra (ethylene oxide) vinyl phenyl ether, ethyl tetra (ethylene oxide) vinyl phenyl ether, propyl tetra (ethylene oxide) vinyl phenyl ether, n-butyl tetra (ethylene oxide) vinyl phenyl ether , N-pentyltetra (ethylene oxide) vinyl phenyl ether, tetra (propylene oxide) vinyl phenyl ether, methyl tetra (propylene oxide) vinyl phenyl ether, ethyl tetra (propylene oxide) vinyl phenyl ether, propoxy tetra (propylene oxide) vinyl phenyl ether N-butyltetra (propylene oxide) vinyl phenyl ether, n Pentaxytetra (propylene oxide) vinyl phenyl ether, poly (ethylene oxide) vinyl phenyl ether, methyl poly (ethylene oxide) vinyl phenyl ether, ethyl poly (ethylene oxide) vinyl phenyl ether, poly (propylene oxide) vinyl phenyl ether, methyl poly (propene Oxide) vinyl phenyl ether, ethyl poly (propylene oxide) ethenyl phenyl ether, poly (ethylene oxide) vinyl benzyl ether, methyl poly (ethylene oxide) vinyl benzyl ether, ethyl poly (ethylene oxide) ethenyl benzyl ether, poly (propylene oxide) vinyl Benzyl ether, methyl vinyl poly (propylene oxide) vinyl benzyl Ether, ethyl poly (propylene oxide) vinyl benzyl ether, poly (ethylene oxide) vinyl phenyl ethyl ether, methyl poly (ethylene oxide) vinyl phenyl ethyl ether, ethyl poly (ethylene oxide) vinyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl ethyl ether Vinyl phenyl ether compounds having a long-chain polyalkylene oxide moiety such as methyl poly (propylene oxide) vinyl phenyl ethyl ether, ethyl poly (propylene oxide) vinyl phenyl ethyl ether;

  For example, isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hexadecyl ether, isopropenyl phenyl Methyl heptadecyl ether, Isopropenyl phenyl having a long chain alkyl group such as isopropenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl heneicosyl ether, isopropenyl phenyl methyl docosyl ether Ether compounds;

  For example, poly (ethylene oxide) isopropenyl phenyl ether, methyl poly (ethylene oxide) isopropenyl phenyl ether, ethyl poly (ethylene oxide) isopropenyl phenyl ether, poly (propylene oxide) isopropenyl phenyl ether, methyl poly (propylene oxide) isopropenyl phenyl Ether, ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethylene oxide) isopropenyl benzyl ether, methyl poly (ethylene oxide) isopropenyl benzyl ether, ethyl poly (ethylene oxide) isopropenyl benzyl ether, poly (propylene oxide) isopropenyl benzyl Ether, methyl poly (propylene oxide) Isopropenyl ether-based compound having a polyalkylene oxide moiety, such as propenyl benzyl ether;

  For example, mono-long-chain alkyl ester-based cyclic vinylphenyl compounds of dicarboxylic acids such as vinylphenylnonyl succinate, vinylphenylmethyldecyl hexahydrophthalate, and vinylphenylethyldodecyl terephthalate;

  For example, vinyl ester compounds having a monopolyalkylene oxide moiety of a dicarboxylic acid such as vinyl phenyl poly (ethylene oxide) succinate, vinyl phenyl methyl poly (ethylene oxide) hexahydrophthalate, vinyl phenyl ethyl poly (ethylene oxide) terephthalate, etc. Kind;

  Polyalkylene oxides such as methyl 4-vinylbenzoate poly (ethylene oxide), ethyl polyvinylbenzoate poly (ethylene oxide), methyl 4-isopropenylbenzoate poly (propylene oxide), ethyl polyisopropylenylbenzoate poly (propylene oxide) Vinyl benzoate or isopropenyl benzoate compounds having a moiety;

  For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

  For example, ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetraconten And alkenes such as polybutene-1, polypentene-1, and poly-4-methylpentene-1;

  For example, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, (meth ) Acrylic acid dimer, maleic acid, fumaric acid, monomethyl maleic acid, monomethyl fumaric acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid, mesaconic acid, itaconic acid, tiglic acid, Angelic acid, senetic acid, crotonic acid, isococrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, gellanic acid, citronellic acid, 4-acrylamidobutanoic acid, 6-acrylamidohexanoic acid, 2- (Meth) acryloyloxyethyl succine , Mono (meth) acrylic acid ω-carboxy polycaprolactone ester, etc., repeating polylactone-based (meth) acrylic acid ester, ethylene oxide, propylene oxide and other alkylene oxides having a carboxyl group at the terminal by ring-opening addition of a lactone ring A carboxyl group-containing aliphatic α, β-unsaturated double bond group-containing carboxylic acid such as an ester of an alkylene oxide-added succinic acid having a carboxyl group at the terminal and (meth) acrylic acid, Its acid anhydrides;

  For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyl Oxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, Carboxylic acids such as cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid and the like, and carboxylic acids containing alicyclic and aromatic rings containing aromatic groups and aromatic rings and acid anhydrides Etc .;

  For example, (meth) acrylic acid cyclic esters containing a sulfo group such as (meth) acrylic acid sulfophenoxyethyl, (meth) acrylic acid sulfocyclohexyl, (meth) acrylic acid sulfobenzyl;

  For example, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- (meth) acryloyloxyoctyl (Meth) acrylic acid cyclic esters containing phthalic acid such as phthalate, 2- (meth) acryloyloxydecyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate;

  For example, aromatics such as 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid Vinyl compounds containing an aromatic carboxylic acid;

  For example, (meth) acryloyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate, phenyl-2- ( Metal salts and ammonium salts of (meth) acrylic acid cyclic esters containing a sulfonyl group such as (meth) acryloyloxyethyl phosphate;

  Examples thereof include sulfonyl group-containing (meth) acrylamides such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid and (meth) acrylamide-2-methyl-1-propanesulfonic acid.

  For example, N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N-propylaminoethyl (meth) acrylate, N-butylaminoethyl (meth) acrylate, (meth) acryl (Meth) acrylic acid esters having a primary or secondary amino group such as N-tributylaminoethyl acid, tetramethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl acrylate;

  For example, (meth) acrylic acid hydrazide, 2- (2-furyl) -3- (5-nitro-2-furyl) (meth) acrylic acid hydrazide, β- (2-furanyl) (meth) acrylic acid N2, N2 -(Meth) acrylic acid esters having a hydrazino group such as bis (2-chloroethyl) hydrazide, N- (m-vinylphenyl) acrylohydrazide;

  For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, 4- (pyrimidine (2-yl) piperazin-1-yl (meth) acrylate (meth) acrylic acid esters having a tertiary amino group;

  For example, imide (meth) acrylate, 2- (4-oxazolin-3-yl) ethyl (meth) acrylate, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone Heterocyclic structures containing oxygen atoms in addition to nitrogen atoms such as modified tris- (2-acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, tri (meth) acrylic acid isocyanuric acid ethylene oxide modification Cyclic amino group-containing (meth) acrylic acid esters having;

  For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (Meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, N, N-dimethyl ( Meta) Acu Luamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N′-dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N- Aliphatic (meth) acrylamides such as vinylmethanamide and N-vinylacetamide;

  For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-iso Roxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) Acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- N-alkoxy group-containing (meth) acrylamides such as 2-methoxyethyl (meth) acrylamide, N, N-di (methoxymethyl) (meth) acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide;

  For example, (meth) acrylamides having a tertiary amino group such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide;

  For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( (Meth) acrylamides having a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

  For example, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl) (Meth) acrylamide, N-[(R) -1-phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, (Z) -N-methyl-3- ( Phenyl) (meth) acrylamide, (Z) -3- (phenyl) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (Meth) acrylamides containing cyclic structures such as (meth) acrylamide

  For example, 4-acryloylmorpholine, N- [2- (1H-imidazol-5-yl) ethyl] (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-2 -Heterocyclic acrylamides such as (ylmethoxymethyl) (meth) acrylamide;

  For example, alkenyl group-containing compounds containing amide groups such as crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itaconamide, 2-methylprop-2-enoylamine, N-vinylmethanamide, N-vinylacetamide;

  For example, alkenyl group-containing compounds having a hydrazino group such as p-vinylbenzhydrazide, 4-vinylbenzenesulfonic acid hydrazide, 2- [2- (5-nitro-2-furyl) vinyl] -4-quinolinecarbohydrazide Kind;

  For example, vinylamine, methylvinylamine, ethylvinylamine, propylvinylamine, butylvinylamine, 2-vinylimidazole, 2-vinylpiperazine, 4-vinylpiperazine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 6-methyl-2-ethenylpyridine, 2-vinylpyrrole, 2-methyl-5-vinyl-1H-pyrrole, 2-vinylpyrazine, 2-methyl-5-vinylpyrazine, 2-methyl-6-vinylpyrazine, 2,5-dimethyl-3-vinylpyrazine, 2-vinylpyrimidine, 2-vinylpyridazine, 2-vinyl-1H-benzimidazole, 2-vinyl-5,6-dimethyl-1H-benzimidazole, 2-vinylindazole, 2-vinylquinoline, 4-vinylquinoline, 2-vinylisoquino Phosphorus, 2-vinylisoxaline, 2-vinylquinoxaline, 2-vinylquinazoline, 2-vinylcinnoline, 2,3-divinylpyridine, 2,4-divinylpyridine, 2,5-divinylpyridine, 2,6- Vinyl compounds having a primary or secondary amino group such as divinylpyridine;

  For example, (meth) allylamine, 4- (meth) allyl-3,5-dimethyl-1H-pyrazole, 5- (1-methylpropyl) -5- (meth) allylpyrimidine, 5- (meth) allyl-5- (Meth) allyl compounds having a primary or secondary amino group such as isopropylpyrimidine, 2- (meth) allylpyridine, 4- (meth) allylpyridine, 3,6-dihydro-4- (meth) allylpyridine, etc. Kind;

  For example, vinyl compounds containing tertiary amino groups such as N-ethyl-N-nitrosovinylamine;

  For example, heterocyclic α, maleimide derivatives having both nitrogen and oxygen atoms, such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. β-unsaturated double bond group-containing compounds;

  For example, 2-vinyl oxazole, 2-phenyl-4-vinyl oxazole, 2-phenyl-5-vinyl oxazole, 5-ethoxy-2-vinyl oxazole, 3-vinyl-5-nitrosoxazole, 2-vinyl-4,5 -It has a heterocyclic structure containing an oxygen atom in addition to a nitrogen atom such as diphenyloxazole, 2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazolin-5-one, 2-vinylbenzoxazole Vinyl group-containing compounds;

  For example, 1-vinylpyrrole, 1-vinyl-2-imidazoline, 1-vinyl-2-methyl-2-imidazoline, 1-vinylimidazole, 1-vinyl-1H-pyrazole, 1-vinyl-3,5-dimethyl- 1H-pyrazole, 3-methyl-5-phenyl-1-vinylpyrazole, 1-vinylindole, 1-vinyl-2-methyl-1H-indole, 1-vinylisoindole, 1-vinyl-1H-benzimidazole, 1 -Vinylindazole, 1-vinylquinoline, 1-vinylisoxaline, 1-vinylquinazoline, 1-vinylcinnoline, 1-vinylcarbazole, 1,1'-divinyl-2,2'-bi (1H-imidazole) N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, 1-vinylpyridin-2 (1H) -one, -Vinyl-2 (1H) -pyridinethione, 1-benzyl-2-vinylpiperazine, 1-benzyl-3-vinylpiperazine, 1,4-dimethyl-3-vinylpiperazine, 2-vinyl-4,6-diamino- Cyclic amino group-containing compounds having a nitrogen atom-containing heterocycle such as 1,3,5-triazine, 3-vinyl-1,2,4,5-tetrazine;

  For example, 1- (meth) allyl-1H-imidazole, 1- (meth) allyl-2-methyl-1H-imidazole, 1- (meth) allyl-3-methyl-1H-imidazol-3-ium, 1- ( (Meth) allyl-3-ethyl-1H-imidazol-3-ium, 5-bromo-1- (meth) allyl-1H-pyrazole, 1- (meth) allylpiperazine, 1- (meth) allyl-5,5- Diethylpyrimidine, N- (meth) allyl-s-triazine-2,4,6-triamine, N- (meth) allyl-4,6-dichloro-1,3-5-triazine-2-amine, 1- ( (Meth) allyl-3,5-dimethyl-1H-pyrazole, 1- (1-methylpropyl) -5- (meth) allylpyrimidine, 1- (meth) allyl-5-isopropylpyrimidine, 1- (meth) a Rupyridine, 1- (meth) allylpyridine, 3,6-dihydro-1- (meth) allylpyridine, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 2- (meta ) Allylindazole, 3-phenyl-4- (meth) allylisoquinoline, 9- (meth) allyl-9H-carbazole, 1- (meth) allyl-3,5-dimethyl-1H-pyrazole, 1- (1-methyl Propyl) -5- (meth) allylpyrimidine, 1- (meth) allyl-5-isopropylpyrimidine, 1- (meth) allylpyridine, 1- (meth) allylpyridine, 3,6-dihydro-1- (meth) Allylpyridine, 2- (meth) allyl-1H-indole, 3- (meth) allyl-1H-indole, 2- (meth) allylindazole, 3-phenyl 4- (meth) allyl isoquinoline, 9- (meth) cyclic amino group containing having a heterocyclic structure of the nitrogen atom-containing and allyl -9H- carbazole (meth) allyl group-containing compounds;

  For example, 1-vinyl-1H-benzimidazole, 1-vinyl-5,6-dimethyl-1H-benzimidazole, 1-vinylindazole, 1-vinylquinoline, 1-vinylquinoline, 1-vinylisoquinoline, 1-vinyliso Xaline, 1-vinylquinoxaline, 1-vinylquinazoline, 1-vinylcinnoline, 1- (meth) allyl-1H-benzimidazole, 1- (meth) allyl-3-methyl-1H-indazole, 1- (meta ) Nitrogen such as allyl-4-methyl-1H-indazole, N- (meth) allylquinolin-4-amine, di (meth) allylquinoline, 1,2-di (meth) allyl-1,2-dihydroisoquinoline Atom-containing heteropolycyclic cyclic amino group-containing vinyl compounds;

  For example, polyfunctional vinyl compounds having a nitrogen atom-containing heterocyclic structure and two or more cyclic amino groups, such as 1-methyl-4,5-divinyl-1H-imidazole;

  For example, 2-vinylthiazol, 4-methyl-5-vinylthiazole, 2-vinylbenzothiazole, 2- [2- (1-naphthyl) vinyl] benzothiazole, 2- [2- (dimethylamino) vinyl] benzo Examples thereof include vinyl group-containing compounds having a heterocyclic structure containing a sulfur atom in addition to a nitrogen atom such as thiazole, but are not particularly limited thereto. These may be used alone or in combination of two or more.

  As the α, β-unsaturated double bond group-containing compound (a2) having no hydroxyl group in the molecule, a compound having a (meth) acryloyl group is preferable from the viewpoint of reactivity, and in particular, a compound having an acryloyl group. It is preferable to include.

  In the α, β-unsaturated double bond group-containing compound (a2) having no hydroxyl group in the molecule, polymerization reactivity, a compound having one or more P-OH described later, or one or more P-OH by hydrolysis Shrinkability in crosslinking and curing with compound (B), silane compound (C) having amino group or epoxy group, and polyisocyanate compound (D), and durability such as heat resistance, moist heat resistance and water resistance From this point, it is possible to synthesize a good copolymer (A) by appropriately blending and polymerizing the monomer mixture so that both the compound (a1) and the compound (a2) are contained in a well-balanced manner. In addition, a better pressure-sensitive adhesive can be obtained.

  The copolymer (A) is a copolymer obtained by copolymerizing the compound (a1) and the compound (a2), and may be expressed as a weight average molecular weight (Mw) of the copolymer (A). ) Is 100,000 to 2,000,000 in order to achieve both the coating suitability of the pressure sensitive adhesive and the cohesive strength of the coating film when the copolymer (A) is used as the pressure sensitive adhesive. It is preferable that it is 200,000 to 1,800,000, more preferably 400,000 to 1,500,000. When the Mw is less than 100,000, the cohesive force of the copolymer (A) may be insufficient and the adhesive force may be reduced. When the Mw exceeds 2,000,000, the viscosity of the copolymer (A) is high. Therefore, the coating property of the pressure-sensitive adhesive may be deteriorated. When Mw is in the above range, the cohesive force and the like are further improved, so that floating and peeling can be further suppressed, and the stress relaxation property is further improved. In addition, the said weight average molecular weight and number average molecular weight are the values of polystyrene conversion measured by the gel permeation chromatography (GPC) method. Details of the GPC measurement method are described in the Examples.

  Further, the hydroxyl value (sometimes referred to as OHV) of the copolymer (A) is determined by the molecular weight and content of the compound (a1), and is in the range of 0.1 to 50 mgKOH / g. It is preferable to adjust the compounding amount of compound (a1), and 0.5 to 30 mgKOH / g is more preferable. When OHV is less than 0.1 mgKOH / g, crosslinking with phosphoric acid or a derivative thereof (B), a silane compound (C) having an amino group or an epoxy group, and a polyisocyanate compound (D), which will be described later, is insufficient. And heat and humidity resistance decrease. On the other hand, if it exceeds 50 mgKOH / g, the crosslinking density with phosphoric acid or its derivative (B), a silane compound (C) having an amino group or an epoxy group, and a polyisocyanate compound (D) described later becomes too high, resulting in poor adhesion In the case of a flexible substrate, the adhesive strength is reduced, and the presence of excess hydroxyl groups reduces durability such as moisture and heat resistance and water resistance.

  In the copolymer (A), an α, β-unsaturated double bond group-containing compound (a1) containing at least one hydroxyl group in the molecule and an α, β-unsaturated double containing no hydroxyl group in the molecule A copolymer (A) obtained by polymerizing a monomer mixture containing a linking group-containing compound (a2) is a monomer of various α, β-unsaturated double bond group-containing compounds as described above according to a conventional method. It is synthesized by a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization using 0.001 to 20 parts by weight of a polymerization initiator with respect to a total of 100 parts by weight of the body mixture. Preferably, it is synthesized by solution polymerization.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) and 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) Dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (1-acetoxy-1-phenylethane), 4,4′-azobis (4-cyanovaleric acid), 2,2′- Examples include azo compounds such as azobis (2-hydroxymethylpropionitrile) and 2,2′-azobis [2- (2-imidazolin-2-yl) propane].

  Also, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxy Organic such as 2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide A peroxide is mentioned.

  In the synthesis, mercaptans such as lauryl mercaptan and n-dodecyl mercaptan, and chain transfer agents such as α-methylstyrene dimer and limonene may be used.

  Among these, from the viewpoint of molecular weight control and molecular weight distribution control, 2,2′-azobisisobutyronitrile, dimethyl 2,2′-azobis (2-methylpropionate), dimethyl 2, 2'-azobisisobutyrate and dibenzoyl dioxydan, tert-butyl perbenzoate, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, octanoyl peroxide, lauroyl peroxide, tert-butyl peroxy 2-Ethylhexanoate is preferred.

  When the copolymer (A) is synthesized by a solution polymerization method, examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol, acetone, methyl ethyl ketone, and methyl-n. -Propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl n-propyl ketone, ethyl isopropyl ketone, ethyl n-butyl ketone, ethyl isobutyl Ketones such as ketones, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, isophorone, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate Isobutyl acetate, hexyl acetate, octyl acetate, methyl lactate, propyl lactate, butyl lactate esters, ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol Glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dipropyl ether, tripropylene glycol monomethyl ether and other glycols and glycol ethers, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether Glycol acetates such as acetate and dipropylene glycol monomethyl ether acetate, saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane and isododecane, 1-hexene, 1-heptene, 1-octene, etc. Saturated hydrocarbons, cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclodecane, decalin, etc., cyclic such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene, cyclododecene, etc. Examples thereof include unsaturated hydrocarbons and aromatic hydrocarbons such as benzene, toluene and xylene. These organic solvents may be used alone or in combination of two or more. The amount of the solvent may be appropriately determined in consideration of the polymerization conditions, the composition of each component of the α, β-unsaturated double bond group-containing compound, the viscosity and concentration of the resulting copolymer (A), A compound having one or more P-OH described later or a compound (B) capable of forming one or more P-OH by hydrolysis, a silane compound (C) having an amino group or an epoxy group, and a polyisocyanate compound (D) It is preferable not to use a solvent having an active hydrogen that can react with the solvent, such as an alcohol solvent.

  What is necessary is just to set suitably the polymerization conditions at the time of synthesize | combining a copolymer (A) according to a polymerization method, and it is not specifically limited. The polymerization temperature is preferably 20 to 150 ° C, more preferably 40 to 120 ° C. The reaction time may be appropriately set so that the polymerization reaction of each component of the α, β-unsaturated double bond-containing compound is completed.

<Compound having one or more P-OH or compound (B) capable of forming one or more P-OH by hydrolysis>
Next, a compound having one or more P—OH or a compound (B) capable of forming one or more P—OH by hydrolysis will be described. A compound having one or more P-OH or a compound (B) capable of forming one or more P-OH by hydrolysis includes phosphoric acid (b1), phosphate such as metal phosphate or ammonium phosphate (b2), phosphonyl A phosphoric acid compound (b3) such as a phosphoric acid ester or phosphoric acid amide containing a group, a phosphinyl group, or a phosphanyl group, and having one or more P—O—H bonds in the molecule or hydrolyzing Examples thereof include compounds capable of forming one or more P—O—H bonds. The compound (B) undergoes addition, substitution, or chelation reaction between the hydroxyl group in the copolymer (A) and the amino group, epoxy group, or siloxy group in the silane compound (C) described later. Causing phosphoric acid esterification and phosphoric acid amidation.

  When the compound (B) is used as a component of the pressure-sensitive adhesive, it is contained in the pressure-sensitive adhesive when the substrate (G) and the adherend to be described later are laminated via the pressure-sensitive adhesive. The compound (B) reacts with amino groups, epoxy groups, or siloxy groups contained in all of the hydroxyl groups and the silane compound (C) described below, including the copolymer (A), to form phosphoric acid ester or phosphoric acid. Amidation proceeds. Therefore, the adhesion to each substrate and adherend is improved, and the heat resistance, moist heat resistance, water resistance, solvent resistance, mechanical strength, electrical insulation, dimensional stability, etc. are significantly improved.

  The compound (B) can be classified into phosphoric acids (b1), phosphates (b2), and phosphoric acid compounds (b3) such as phosphoric esters and phosphoric amides. Examples of the phosphoric acid (b1) include orthophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, phosphinic acid, peroxo-phosphoric acid, polyphosphoric acid, diphosphorus pentoxide, tetraphosphorus hexaoxide, and tetraphosphorus octaoxide. And phosphoric acids such as

Examples of the phosphate (b2) include calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, potassium phosphate (eg, potassium metaphosphate, potassium tetraphosphate, potassium pentaphosphate, potassium octaphosphate), sodium phosphate (eg, peroxyphosphate) Metal phosphates such as sodium phosphate, sodium metaphosphate, sodium tetraphosphate, sodium pentaphosphate, sodium hexaphosphate and sodium octaphosphate), zinc phosphate;
Examples thereof include ammonium phosphates such as diammonium hydrogen phosphate and diammonium phosphate.

  Examples of the phosphoric acid compound (b3) include phosphoric acid esters, phosphoric acid amides, alkyl phosphates, and the like. Examples of the phosphoric acid esters include phosphoric acid esters obtained by reaction of phosphoric acid with alcohols or phenols. Examples of the phosphate ester include monobutyl phosphate, monoamyl phosphate, monononyl phosphate, monophenyl phosphate, monobenzyl phosphate, trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, tri-n-butyl phosphate (TSP), and triphenyl phosphate. , Phosphates such as triisopropyl phosphate, monocyclohexyl phosphate, tri-2-cyclohexyl phosphate, triisopropylamine phosphate, mannitol phosphate, monopyridine phosphate and glycerol phosphate, polyoxyalkylene phosphate ester;

  For example, phosphoric acid amides include phosphoric acid amides obtained by reaction of phosphoric acid with amines. Examples include phosphoric acid triethanolamine, phosphoric acid tri-t-amyl, phosphoric acid triisopropanolamine, ethylenediamine phosphate melamine salt, piperazine pyrophosphate. Melamine salt of ethylenediamine polyphosphate, melamine salt of piperazine phosphate, melamine salt of piperazine polyphosphate, melamine phosphate, melamine phosphate polyphosphate, piperazine phosphate phosphate, ethylenediamine phosphate etc. And phosphoric acid amides.

  These may be used singly or in combination of two or more, but the hydroxyl group contained in the copolymer (A) and the ease of interaction with the silane compound (C) described later It is preferable to use phosphoric acids (b1). The phosphoric acid (b1) interacts with the hydroxyl group contained in the copolymer (A) and the silane compound (C) described later, so that when used as a component of the pressure-sensitive adhesive, the phosphoric acid (b1) Due to the formation of pseudo-crosslinks, the bleeding from the coating film is not suppressed even in harsh environments, but the pressure-sensitive adhesive created from the pressure-sensitive adhesive of the present invention to an adherend having a polarity such as glass. When a film is bonded, it is preferable because adhesion can be improved. Of these, orthophosphoric acid, metaphosphoric acid, and polyphosphoric acid are preferably used.

  The content ratio of the compound (B) is preferably such that the molar ratio of the phosphorus atom in the compound (B) to the hydroxyl group in the copolymer (A) is 0.5 to 1.5, and 1.0 to 1 .3 is more preferable, and 1.05-1.2 is most preferable. As described above, when the molar ratio of the phosphorus atom to the hydroxyl group is 0.5 or more and less than 1.5, the phosphoric acid esterification to the hydroxyl group is sufficiently performed, and a crosslinked coating film having high cohesive force is obtained. Thermal properties are improved.

<Silane compound (C) having amino group or epoxy group>
Next, the silane compound (C) having an amino group or an epoxy group will be described.
The silane compound (C) having an amino group or an epoxy group means a silane compound (c1) having an amino group or a silane compound (c2) having an epoxy group. The amino group contained in the silane compound (c1) forms a salt with the phosphoric acid group of the compound having one or more P-OH or the compound (B) capable of forming one or more P-OH by hydrolysis, In addition, since the epoxy group contained in the silane compound (c2) forms a bond by addition reaction with the phosphoric acid group of the above-described phosphoric acid or its derivative (B), the silane compound (C ), And the fixability of the silane compound in the coating film can be improved, so that the characteristics of the original silane compound are easily exhibited.
Moreover, the amino group or epoxy group contained in the silane compound (C) causes a crosslinking reaction with the isocyanate group contained in the polyisocyanate compound (D) described later, and is also contained in the silane compound (C). A siloxy group causes a crosslinking reaction with a hydroxyl group contained in the copolymer (A) or the base material (G) described later, and a strong mutual bond is formed between the pressure-sensitive adhesive and the base material (G) or the adherend. It is also possible to express the action.

  More specifically, examples of the silane compound (c1) having an amino group include N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and N- (2-amino). Methyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, Amino-based alkoxysilanes such as N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane hydrochloride;

For example, trimethylsilyldimethylamine, trimethylsilyldiethylamine, dimethylaminotrimethylsilane, allylaminotrimethylsilane, N-methyl-N-trimethylsilylacetamide, anilinotrimethylsilane, 1-trimethylsilylpyrrole, 1-trimethylsilylpyrrolidone, 1-trimethylsilylimidazole, 1- Silylamines having a monofunctional silylamino group such as trimethylsilyl-1,2,4-triazole;
1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, N, N′-bis (trimethylsilyl) -N-phenyl Silylamines having a bifunctional silylamino group such as urea;
Has a tri- or higher functional cyclic silylamino group such as 1,1,3,3,5,5-hexamethylcyclotrisilazane and 1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane And silylamines.

  More specifically, examples of the silane compound (c2) having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β -(3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) Epoxy alkoxysilanes such as ethylmethyldiethoxysilane are exemplified.

  The silane compound (C) having an amino group or an epoxy group exemplified here may be used alone or in combination with a plurality of compounds, and is not particularly limited thereto. Examples of the silane compound (c1) having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, and N- (2-amino). Methyl) 3-aminopropyltrimethoxysilane is preferably used, and as the silane compound (c2) having an epoxy group, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, γ-glycid Xylpropyltriethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferably used.

<Polyisocyanate compound (D)>
Next, the polyisocyanate compound (D) will be described.
The polyisocyanate compound (D) has a role of cross-linking with the hydroxyl group of the copolymer (A), improving the cross-linking molecular weight of the pressure-sensitive adhesive, and improving the cohesive force. In addition, the compound (D) can be expected to have an effect of improving the interaction such as chemical reaction or physical adsorption with polar groups or adhering water present on the surface of the substrate (G) described later. Furthermore, for a base material that has been subjected to physical treatment such as corona discharge treatment or chemical treatment that has been modified with an acid or the like, a chemical reaction or investment between the isocyanate group in the compound (D) and the base material (G). Due to the effects and the like, it is possible to cause a strong interaction between the copolymer (A) and the base material (G).

The polyisocyanate compound (D) is not particularly limited as long as it is a compound having at least two isocyanate groups in the molecule.
The polyisocyanate compound (D) is classified into aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate and the like.

  Among the polyisocyanate compounds (D), as the aliphatic polyisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like.

  More specifically, examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, and 2,4-tolylene diisocyanate (alias: 2,4- TDI), 2,6-tolylene diisocyanate (also known as 2,6-TDI), 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether Diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, 1,3-phenylene bismethylene diisocyanate (also known as m-XDI), 1,4-phenylene bismethylene diisocyanate (also known as p-XDI) ), 2,2′-diphenylmethane diisocyanate (Also known as 2,2-MDI), 4,4'-diphenylmethane diisocyanate (also known as 4,4-MDI), 1,3-naphthalenediyl diisocyanate (also known as 1,3-NDI), 1,5-naphthalene And diyl diisocyanate (alias: 1,5-NDI).

  As alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Mention may be made of methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, norbornene diisocyanate and the like.

  Further, as part of the compound (D) component, the above-mentioned adducts of polyisocyanate with polyols such as 2-methylpentane-2,4-diol and trimethylolpropane, trimers having an isocyanurate ring, etc. are also used. can do. Polyphenylmethane polyisocyanate (also known as PAPI), and these polyisocyanate-modified products can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretonimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups. Moreover, the polyisocyanate compound (D) can also use the blocked isocyanate which blocked the isocyanate group using the blocking agent.

  When the polyisocyanate compound (D) is used, a known catalyst can be used as necessary for promoting the reaction between the hydroxyl group of the copolymer (A) and the isocyanate group. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned, and it may be used alone or in combination.

  Examples of tertiary amine compounds include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU), and these may be used alone or in combination. You can also

Examples of organometallic compounds include tin compounds and non-tin compounds.
Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyl Examples thereof include tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.
Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, 2- Iron-based such as iron ethylhexanoate and iron 2,4-pentadionate, cobalt-based such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc-based such as zinc naphthenate and zinc 2-ethylhexanoate, naphthene Examples thereof include zirconium acid.
Among the above catalysts, dibutyltin dilaurate (also known as DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  The polyisocyanate compound (D) exemplified herein may be used alone or in combination with a plurality of compounds, and is not particularly limited thereto. It can also be used in combination with a high molecular weight polycarbodiimide compound, a polyfunctional aziridine compound, a metal chelate compound, and the like. As the polyisocyanate compound (D), particularly in terms of crosslinking reactivity, it was added to adducts of diisocyanates such as HDI, TDI, MDI, and IPDI with trimethylolpropane, burettes reacted with water, and isocyanurate rings. Trimers are preferably used.

  The pressure-sensitive adhesive of the present invention is a compound having one or more P-OH or hydroxyl group of the copolymer (A) or a hydroxyl group in the copolymer (A) or P-OH by hydrolysis. In consideration of the molar ratio of phosphorus atoms in the compound (B) that can form one or more, 0.01 to 10 weight percent of phosphoric acid or its derivative (B) with respect to 100 weight parts of the copolymer (A). Preferably 0.01 to 10 parts by weight of a silane compound (C) having an amino group or an epoxy group, and 0.1 to 30 parts by weight of a polyisocyanate compound (D). 0.1 to 8 parts by weight of a compound having one or more or a compound (B) capable of forming one or more P-OH by hydrolysis, 0.1 to 8 parts by weight of a silane compound (C), and a polyisocyanate compound (D) 0.5 to 20 layers It is further preferred that comprising parts. If the compound (B) is 0.01 parts by weight or more and less than 10 parts by weight, the effect of improving heat resistance and heat and humidity resistance can be expected. Furthermore, since the acidity is not so high, hydrolysis of the base material and corrosion Occurrence hardly occurs, and it is possible to maintain the adhesive force. Further, when the silane compound (C) having an amino group or an epoxy group is 0.01 parts by weight or more and less than 10 parts by weight, a high cohesive force accompanying crosslinking with the compound (B) or the polyisocyanate compound (D). Therefore, it is possible to expect sufficient adhesive force and an improvement effect of heat resistance and moist heat resistance of the crosslinked coating film. Furthermore, since the stability of the solution accompanying the coexistence with the compound (B) and the polyisocyanate compound (D) is also improved, the pot life can be extended, which is useful. Furthermore, when the polyisocyanate compound (D) is 0.1 parts by weight or more and less than 30 parts by weight, the crosslinking density of the coating film is improved, so that the Tg of the pressure-sensitive adhesive is increased, and heat resistance and heat and humidity resistance are increased. Is further improved, and “floating / peeling” of the coating film is suppressed.

<Silane compound having no amino group or epoxy group (E)>
Next, the silane compound (E) having no amino group or epoxy group will be described.
In one embodiment of the pressure-sensitive adhesive of the present invention, the pressure-sensitive adhesive may contain a silane compound (E) having no amino group and no epoxy group in addition to the essential components. By using the silane compound (E) in combination with the silane compound (C), a self-condensation reaction between the silane compounds may occur, or chemical reaction may occur between the substrate (G) surface and the polar group on the adherend surface. Interaction of physical reaction and physical adsorption is expressed, and the adhesive force of the pressure sensitive adhesive can be improved. In particular, since the interaction of chemical reaction and physical adsorption is high on the surface of an inorganic material such as glass, metal foil, metal vapor deposition film, metal plate, or inorganic filler-containing film, it is easy to improve the adhesive strength. .

  As a silane compound (E) which does not have an amino group and an epoxy group, a known silane compound can be used, and in particular, as long as adhesion with a substrate (G) or an adherend described later is improved. It is not limited. For example, alkyl alkoxysilane, aryl alkoxysilane, carbamate alkoxysilane, vinyl alkoxysilane, halogen alkoxysilane, (meth) acryloyl alkoxysilane, mercapto alkoxysilane, imidazole alkoxysilane, isocyanate alkoxysilane, etc. And alkoxysilanes having an alkoxyl group, or organic silanes having reactivity by directly bonding a hydrogen atom to a silicon atom.

  More specifically, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriacetoxysilane, methyltris (methoxyethoxy) silane, methyltris ( Methoxypropoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxy Silane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriet Xysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiacetoxysilane, dimethylbis (methoxyethoxy) silane, dimethylbis (methoxypropoxy) silane, diethyldimethoxy Silane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldiacetoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldiisopropoxysilane, methylethyldiacetoxysilane, methylpropyldimethoxysilane, methylpropyldi Alkyl series such as ethoxysilane, methylpropyldiisopropoxysilane, methylpropyldiacetoxysilane, etc. Kokishishiran the like;

  For example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriacetoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldi Aryl alkoxysilanes such as acetoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiisopropoxysilane, methylphenyldiacetoxysilane;

For example, (3-carbamateethyl) propyltriethoxysilane, (3-carbamateethyl) propyltrimethoxysilane, (3-carbamateethyl) propyltripropoxysilane, (3-carbamatepropyl) propyltriethoxysilane, (3-carbamatepropyl ) Propyltrimethoxysilane, (3-carbamatepropyl) propyltripropoxysilane, (3-carbamatebutyl) propyltriethoxysilane, (3-carbamatebutyl) propyltrimethoxysilane, (3-carbamatebutyl) propyltripropoxysilane, (3-carbamatebutyl) butyltripropoxysilane, (3-carbamatebutyl) propylmethyldiethoxysilane, (3-carbamatepentyl) propyltriethoxysilane (3-carbamatehexyl) propyltriethoxysilane, 3-carbamateoctyl) pentyl riboxysilane, (3-carbamateethyl) propylsilyltrichloride, (3-carbamateethyl) propyltrimethylsilane, (3-carbamateethyl) propyldimethyl Carbamate alkoxysilanes such as silane, (3-carbamateethyl) propyltributylsilane, (3-carbamateethyl) ethyl-p-xylenetriethoxysilane, (3-carbamateethyl) -p-phenylenetriethoxysilane;

  For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinyltris (methoxyethoxy) silane, vinyltris (methoxypropoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, divinyldimethoxysilane , Divinyldiethoxysilane, divinyldiisopropoxysilane, divinyldiacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldiisopropoxysilane, methylvinyldiacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, Diallyldiisopropoxysilane, methylallyldimethoxysilane, methylallyldiethoxysilane, methylallyldiisopropoxy Vinyl alkoxysilanes such as silane and methylallyldiacetoxysilane;

  For example, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3-chloropropylmethyldiethoxysilane, 3,3,3-trifluoropropyltrimethoxy Halogen-based alkoxysilanes such as silane, 3,3,3-trifluoropropyltriethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane Kind;

  For example, 3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- (Meth) acryloyl alkoxysilanes such as acryloxypropylmethyldimethoxysilane;

  For example, mercapto-based alkoxysilanes such as 3-mercaptopropyltrimethoxylane, 3-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane;

  For example, imidazole alkoxysilanes such as 3- (2-imidazolin-1-yl) propyltrimethoxysilane and 3- (2-imidazolin-1-yl) propyltriethoxysilane;

Examples thereof include isocyanate-based alkoxysilanes such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropyltripropoxysilane.

  For example, methylsilane, ethylsilane, dimethylsilane, diethylsilane, diethylmethylsilane, butyldimethylsilane, di-t-butylmethylsilane, triethylsilane, trihexylsilane, butyldimethylsilane, cyclohexyldimethylsilane, n-hexylsilane, n- Octylsilane, tri-n-octylsilane, tripropylsilane, triisopropylsilane, triisobutylsilane, trihexylsilane, n-octadecylsilane, phenylsilane, methylphenylsilane, dimethylphenylsilane, methylphenylvinylsilane, dimethylbenzylsilane, Diphenylsilane, triphenylsilane, (phenylethynyl) dimethylsilane, methyldichlorosilane, ethyldichlorosilane, dimethylchlorosilane, bis ( -Chloroethoxy) methylsilane, tris (2-chloroethoxy) silane, n-hexyldichlorosilane, diisopropylchlorosilane, dichlorosilane, di-t-butylchlorosilane, trichlorosilane, chloromethylsilane, methylphenylchlorosilane, phenyldichlorosilane, diphenyl Chlorosilane, chloroisopropylsilane, dichloromethylsilane, dichloroethylsilane, methyldimethoxysilane, dimethoxymethylsilane, methyldiethoxysilane, dimethylethoxysilane, diethoxysilane, trimethoxysilane, triethoxysilane, tripentyloxysilane, tris ( Trimethylsiloxy) silane, methylphenylethenylsilane, allyldimethylsilane, 1,1,2-trimethyldisilane, 1,1,2, -Tetraphenyldisilane, 1,1,3,3-tetramethyldisilazane, 1,4-bis (dimethylsilyl) benzene, methyltris (dimethylsiloxy) silane, tris (trimethylsiloxy) silane, phenyltris (dimethylsiloxy) silane , Tetrakis (dimethylsiloxy) silane, tetramethyldisilazane, dimethylsilyldimethylamine, bis (dimethylamino) methylsilane, tris (dimethylamino) silane, tris (dimethylsilyl) amine, N, N-dimethylaminomethylethoxysilane, di Acetoxymethylsilane, N, O-bis (dimethylsilyl) acetamide, 2- (dimethylsilyl) pyridine, methyltris (1H-imidazol-1-yl) silane, tetrakis (dimethylsilyl) silane, allyldimethylsilane Lan, mercaptodimethylsilane, cyclopropanesilane, tris (trimethylsilyl) silane, 1,1,4,4-tetramethyldisilylethene, cyclohexanesilane, pentamethyldisiloxane, tetramethylcyclotetrasiloxane, 1,3-diphenyl- 1,3-dimethyldisiloxane, pentamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3-tetrakis (trimethyl) Siloxy) disiloxane, 1,1,3,3, -tetramethyldisilazane, 1,2-bis (dimethylsilyl) benzene, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1 , 3,3,5,5,7,7-octamethyltetrasiloxane, 1,1,1,3,5,5,5 Heptamethyltrisiloxane, 1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,3,5,7 -Tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,2,3,4,5,6-hexamethylcyclotrisilazane, α, ω-bis (hydrodiene) Examples thereof include polydimethylsiloxane and long-chain dimethylsiloxane oligomers and oily or waxy organic silanes having a silyl group.

  Moreover, as this silane compound (E), it is also possible to use a commercial product, and it is also possible to use an oligomer silane obtained by oligomerizing a mixture of two or more silanes by hydrolysis and condensation. The silane compound (E) may be used alone or in combination of two or more. In particular, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- Mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3- (2-imidazolin-1-yl) propyltriethoxysilane, and 3-isocyanatopropyltriethoxysilane are preferably used.

  The pressure-sensitive adhesive of the present invention preferably contains 0.1 to 5 parts by weight of the silane compound (E) with respect to 100 parts by weight of the copolymer (A). If it is 0.1 parts by weight or more, the heat resistance and heat-and-moisture resistance are improved, and if it is less than 5 parts by weight, the coating film can be prevented from floating, peeling, or foaming in a harsh environment. Suitable for (G) and adherence to and adherend.

<Epoxy compound (F)>
Next, the epoxy compound (F) will be described.
In one embodiment of the pressure-sensitive adhesive of the present invention, the pressure-sensitive adhesive may contain an epoxy compound (F) (excluding those belonging to the silane compound (c2)) in addition to the essential components. . By using the compound (F), combined crosslinking is possible, so that the cured coating film can be hardened, and it becomes easy to improve heat resistance or heat and humidity resistance in a harsh environment.

  As the epoxy compound (F), a compound having two or more three-membered cyclic epoxy groups (also referred to as oxirane groups) is preferable. More specifically, for example, 2,2-bis (hydroxyphenyl) propane / 2-chloromethyloxirane type oxirane resins, 2,2-bis (hydroxyphenyl) methane type, 2,2-bis (4-hydroxy) Phenyl) ethane type, 2,2-bis (4-hydroxyphenyl) butane type, 4,4′-sulfonyldiphenol type, 1,1-dichloro-2,2-bis (4-hydroxyphenyl) ethene type, 1 , 3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene type, 2,2-bis (4-hydroxy-3-methylphenyl) propane type, 2,2-bis (4-hydroxy-3) -Methylphenyl) methane type, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane type, 2,2-bis (4-hydroxy-3,5-dimethyl) Enyl) propane type, 2,2-bis (4-hydroxycyclohexyl) propane type, 2,2-bis (2-hydroxy-5-biphenylyl) propane type and copolymerized oxirane resins, phenol novolac type , Orthocresol novolak type, para tertiary butylphenol novolak type, paraoctylphenol novolak type, nonylphenol novolak type and co-condensation type oxirane resins, ethylene oxide diglycidyl ether, polyethylene oxide diglycidyl ether, glycerin diglycidyl ether, glycerin Triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N ′, N′— Aliphatic or aromatic oxirane compounds such as traglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, or glycidyl ether, glycidyl ester, glycidylamine, etc. Oxirane group-containing compounds in which part of the hydrogen atom of the epoxy ring (also referred to as oxirane ring) is substituted with a methylene linking group or a methine linking group;

  For example, 1-methyl-3- (2-methyloxiran-2-yl) -7-oxabicyclo [4.1.0] heptane, 1,4-bis (oxiranylmethoxymethyl) cyclohexane, 2,2 ′ -[(1-methylethylidene) bis (4,1-cyclohexanediyloxymethylene)] bisoxirane, 2-[{4- (oxirane-2-ylmethoxy) cyclohexyl} methoxy] oxirane, 2,2 ′-([( Oxirane group-containing compounds having a cycloalkane ring such as propane-2,2-diylbis (cyclohexane-4,1-diyl)) bis (oxy) bis (methylene)]) bis (oxirane);

For example, 3 ′, 4′-oxiranecyclohexylmethyl-3,4-oxiranecyclohexanecarboxylate, 3,4-oxirane-6-methylcyclohexylmethyl-3,4-oxirane-6-methylcyclohexanecarboxylate, bis (3,4 4-oxiranecyclohexylmethyl) adipate, bis (7-oxabicyclo [4.1.0] heptan-3-ylmethyl) adipate, bis (3,4-oxirane-6-methylcyclohexylmethyl) adipate, bis (7-oxa Bicyclo [4.1.0] heptan-3-ylmethyl) carbonate, diethylene glycol bis (3,4-oxiranecyclohexyl methyl ether), ethylene glycol bis (3,4-oxiranecyclohexyl methyl ether), 2,3,14,15 -Geoki Silane-7,11,18,21-tetraoxatrispiro- [5.2.2.5.2.2] henicosane (also 3,4-oxiranecyclohexanespiro-2 ′, 6′-dioxanespiro-3 '', 5 ''-dioxane spiro-3 '' ', 4' ''-oxirane cyclohexane compound), 4- (3,4-oxiranecyclohexyl) -2,6-dioxa-8,9-oxirane An alicyclic group in which an oxirane ring is directly bonded to an alicyclic ring having no aromatic ring, such as spiro [5.5] undecane, 4-vinylcyclohexenedioxide, bis-2,3-oxiranecyclopentyl ether, and dicyclopentadiene dioxide. Oxirane group-containing compounds;

For example, 1,2-phenylenebis (methylene) bis (7-oxabicyclo [4.1.0] heptane-3-carboxylate), 1,3-phenylenebis (methylene) bis (7-oxabicyclo [4. 1.0] heptane-3-carboxylate), 1,4-phenylenebis (methylene) bis (7-oxabicyclo [4.1.0] heptane-3-carboxylate), 1-phenylethane-1,2 -Diylbis (7-oxabicyclo [4.1.0] heptane-3-carboxylate), O ' ³ , O ³ -1,4-phenylenebis (methylene) 4-dibutylbis (7-oxabicyclo [4.1 .0] heptane-3,4-dicarboxylate), bis (7-oxabicyclo [4.1.0] heptane-3-ylmethyl) isophthalate, bis [2-{(7-oxabicyclo [4 1.0] heptane-3-carbonyl) oxy} ethyl] terephthalate, 1,2-bis {(7-oxabicyclo [4.1.0] heptan-3-ylmethoxy) methyl} benzene, 1,3-bis { (7-oxabicyclo [4.1.0] heptan-3-ylmethoxy) methyl} benzene, 1,4-bis {(7-oxabicyclo [4.1.0] heptan-3-ylmethoxy) methyl} benzene, [{Propane-2,2-diylbis (4,1-phenylene)} bis (oxy)] bis (ethane-2,1-diyl) bis (7-oxabicyclo [4.1.0] heptane-3-carboxy Rate), 2,2 ′-(isopropylidenebis-4,1-phenylenebisoxybismethylene) bisoxirane, 2,2 ′-[methylenebis (2,1-phenyleneoxymethylene)] bisoxy Alicyclic oxirane group-containing compounds oxirane ring alicyclic ring directly bonded to an aromatic ring such emissions, and the like.

  The epoxy compound (F) exemplified here may be used alone or in combination with a plurality of compounds, and is not particularly limited thereto.

  The epoxy compound (F) is preferably blended in an amount of 0.1 to 100 parts by weight of the compound (F) based on 100 parts by weight of the copolymer (A). More preferably, it is 1 to 50 parts by weight. By setting the compound (F) to 0.1 parts by weight or more, the lack of cohesive force can be improved, and characteristics such as heat resistance and moist heat resistance can be easily improved. On the other hand, when the compound (F) is 100 parts by weight or less, when used as a pressure-sensitive adhesive, it is easy to obtain an effect in improving the crosslinking rate and cohesive force.

<Other components (Q)>
In one embodiment of the pressure-sensitive adhesive of the present invention, other components (Q) may be appropriately blended with the pressure-sensitive adhesive in addition to the essential components as long as the effects of the present invention are not impaired. Is also possible.
Other components (Q) include, for example, polymerization curing shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, and coloring improvement. From the viewpoint, an organic or inorganic filler can be blended. Such fillers may be composed of materials such as polymers, ceramics, metals, metal oxides, metal salts, and dyes and pigments. Moreover, about the shape, it is not specifically limited, For example, a particulate form, fibrous form, etc. may be sufficient. In addition, when blending the above polymer-based materials, flexibility imparting agent, plasticizer, flame retardant, storage stabilizer, antioxidant, ultraviolet absorber, thixotropy imparting agent, dispersion stabilizer, fluidity imparting It is also possible to dissolve, semi-dissolve or micro-disperse in pressure sensitive adhesives as polymer blends or polymer alloys rather than as independent fillers such as adhesives, tackifiers, antistatic agents and antifoaming agents. .

<Pressure sensitive adhesive>
Next, the pressure sensitive adhesive will be described.
The pressure-sensitive adhesive of the present invention comprises an α, β-unsaturated double bond group-containing compound (a1) containing one or more hydroxyl groups in the molecule and an α, β-unsaturated diester containing no hydroxyl group in the molecule. A copolymer (A) obtained by polymerizing a monomer mixture containing the heavy bond group-containing compound (a2) and having a weight average molecular weight of 100,000 to 2,000,000 and a hydroxyl value of 0.1 to 50 mgKOH / g. And phosphoric acid and derivatives thereof (B), a silane compound (C) having an amino group or an epoxy group, and a polyisocyanate compound (D). If necessary, a silane compound (E ), An epoxy compound (F), or other component (Q).

  It is preferable that the viscosity of the pressure-sensitive adhesive of the present invention is appropriately adjusted according to the usage form. The pressure-sensitive adhesive of the present invention substantially contains an organic solvent, and a solvent may be additionally used as necessary to adjust the viscosity. For example, as a solvent, organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene, and other hydrocarbon solvents as described above, or water are used. Can be used. By using such a solvent, the viscosity of the pressure-sensitive adhesive can be easily adjusted. However, it is preferable not to use a solvent having active hydrogen that can react with the silane compound (C), polyisocyanate compound (D), or silane compound (E), for example, an alcohol solvent. Further, the viscosity can be lowered by heating the pressure-sensitive adhesive without using an additional solvent.

  Using the pressure-sensitive adhesive of the present invention, a pressure-sensitive adhesive layer typically having a film thickness of 0.5 to 300 μm is formed. Furthermore, 1-100 micrometers is more preferable. When the film thickness is in the above range, a sufficient adhesive force can be obtained. Therefore, from the viewpoint of coating film formation, the viscosity of the pressure-sensitive adhesive is desirably in the range of 500 to 8,000 mPa · s, and preferably in the range of 1,000 to 5,000 mPa · s. When the viscosity is 8,000 mPa · s or less, a thin film of 0.5 to 300 μm can be easily formed on the base material (G) by coating, and optical properties such as transmittance can be easily improved. It is. On the other hand, when the viscosity is 500 mPa · s or more, it is easy to control the thickness of the resin layer formed from the pressure-sensitive adhesive. In this embodiment, the film thickness, viscosity, or non-volatile content of the adhesive layer is set according to the use of the laminate.

<Pressure-sensitive adhesive film>
Next, the pressure sensitive adhesive film will be described.
The pressure-sensitive adhesive film of the present invention is obtained by forming a pressure-sensitive adhesive layer made of the above-mentioned pressure-sensitive adhesive on the substrate (G) described later. As a method for producing a pressure-sensitive adhesive film, for example, a pressure-sensitive adhesive is applied to the release-treated surface of a sheet-like substrate (also referred to as a release liner) whose surface has been subjected to a release treatment, and then the substrate (G) is bonded. Or a method in which the pressure-sensitive adhesive is directly applied to the substrate (G) and dried, and the release treatment surface of the release liner is bonded to the surface of the adhesive layer.

  As the substrate (G), it is preferable to use a sheet-like substrate. Specific examples of the sheet-like substrate include cellophane, various plastic sheets, and paper sheets. Of these, the use of various transparent plastic sheets is preferred. Further, the substrate (G) may have a single layer structure, or may have a multilayer structure formed by laminating a plurality of substrates, and is a sheet-like substrate having any structure. Can also be suitably used. When constituting the pressure-sensitive adhesive film of the present invention, it is preferable to form a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive of the present invention on at least one surface of various plastic sheets. Further, a sheet-like substrate (also referred to as a release liner) whose surface has been subjected to a release treatment can be used.

  The various plastic sheets are also referred to as various plastic films, and it is preferable to use various transparent plastic films (also referred to as transparent film (H)). Specific examples of the transparent film (H) include, for example, a polyvinyl alcohol film (also referred to as PVA film), a polytriacetyl cellulose film (also referred to as TAC film), a polypropylene film (also referred to as PP film), and a polyethylene film (PE film). Polyolefin resin film such as polycycloolefin film (also referred to as COP film), ethylene-vinyl acetate copolymer film (also referred to as EVA film), polyethylene terephthalate film (also referred to as PET film) and polybutylene terephthalate Films of polyester resin such as film (also referred to as PBT film), film of polycarbonate resin (also referred to as PC film), film of polynorbornene resin Film, polyarylate resin film, polyacrylate resin film, polyphenylene sulfide resin film (also referred to as PPS film), polystyrene resin film (also referred to as PST film), polyamide resin film (PA film) Also a polyimide resin film (also referred to as a PI film), an oxirane resin film, and the like. Among these substrates, it is particularly preferable to use a sheet-like substrate such as a PVA film, a TAC film, a COP film, a polyester resin film, or a PC film as the transparent film (H).

  In addition, the transparent film (H) has a surface with physical treatment such as corona discharge, plasma treatment, flame treatment, etc., chemical treatment that modifies the film surface with acid or alkali, etc. Films with a substantial increase in surface area of the substrate, or metal oxides such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, yttrium on the surface, or non-metallic inorganic oxides For the pressure-sensitive adhesive, such as a plastic film on which is vapor-deposited, one that has been subjected to an easy adhesion treatment or one that has been provided with functionality for each application can be suitably used.

In the present invention, for the purpose of optical use, an optical film (I) in which a transparent film (H) is used as a substrate (G) and an adhesive layer made of a pressure-sensitive adhesive is formed on the transparent film (H). It is also possible. Here, with the optical film (I), the transparent film (H) can be used as it is as the optical film (I), and the transparent film itself having a special function is used. Is also possible. Here, the special function is intended to have optical functions such as light transmission light diffusion, light collection, refraction, scattering, and HAZE. These transparent films (H) can be used alone or in combination of several kinds when used as the optical film (I). In the present invention, an optical layered body can be formed by forming an adhesive layer made of the pressure-sensitive adhesive on at least one surface of the optical film (I), and the display is laminated on a liquid crystal cell or the like. It can also be used for applications.

Examples of the optical film (I) used in the present invention include a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film.
For example, a polarizing film is also called a polarizing plate, and a polycycloolefin film that is a polynorbornene film, a polyacrylate resin film, a polycarbonate film, or a polyester film on one or both surfaces of a polyvinyl alcohol polarizer. A multilayer structure film in which films such as films are laminated. In the case of a polarizing film, even when left in a high-temperature atmosphere and a high-temperature and high-humidity atmosphere, the adhesive layer according to the present invention has good stress relaxation properties, so that light leakage caused by warping of the polarizing film can be suppressed.

  After applying a pressure-sensitive adhesive to the release liner or optical film (I) by an appropriate method according to a conventional method, if the pressure-sensitive adhesive contains a liquid medium such as an organic solvent or water, heating, etc. If the liquid medium is removed by the method or if the pressure-sensitive adhesive does not contain the liquid medium to be volatilized, the adhesive layer in the molten state is cooled and solidified to adhere onto the release liner or optical film. A layer can be formed. When an adhesive layer is formed on the release liner, the adhesive layer surface and the optical film (I) are bonded together, and the adhesive layer is transferred onto the optical film (I) to adhere to the optical film (I). A layer can be formed.

  The method for applying the pressure-sensitive adhesive of the present invention is not particularly limited. For example, various well-known methods such as Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, kiss coater, lip coater, comma coater, blade coater, knife coater, reverse coater, spin coater, dip coater, etc. Can be applied. Moreover, it can select without particular restriction | limiting also about forms, such as thin film coating or thick film coating.

  The optical laminate of the present invention is obtained by sequentially laminating a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive of the present invention and glass using the optical film (I) as a base material (G). Here, the optical film (I) is preferably a polarizing film. The glass may be the glass surface of a liquid crystal cell.

  The pressure-sensitive adhesive sheet of the present invention has been described by taking a polarizing film as an example of the optical film (I). However, it is not limited to the polarizing film, and it should be easily understood that a laminated body that can be suitably used in optical applications can be configured in other embodiments using other various substrates. For example, it can be preferably used for various electronics-related members such as liquid crystal displays, plasma displays, touch panels, electrode peripheral members, glass members such as protective films, building materials and vehicle window glass, but plastics such as polyolefin, ABS, polyacryl, cardboard It can also be used for metals such as wood, plywood, stainless steel and aluminum.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

Production of copolymer (A) (Synthesis Example 1)
A polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, a polymerization tank and a dropping device of a polymerization reaction apparatus equipped with a nitrogen introduction tube, the following monomers {α containing one or more hydroxyl groups in the molecule, β-unsaturated double bond group-containing compound (a1) and α, β-unsaturated double bond group-containing compound (a2)} not containing a hydroxyl group in the molecule, a polymerization initiator, and an organic solvent in the following ratios: Prepared with.

[Polymerization tank]
N-butyl acrylate (a2-1) 39 parts methyl acrylate (a2-2) 20 parts 2-hydroxyethyl acrylate (a1-1) 1 part acetone (organic solvent) 33 parts V65 (polymerization initiator) 0. 1 part [Drip device]
N-butyl acrylate (a2-1) 39 parts 2-hydroxyethyl acrylate (a1-1) 1 part Acetone (organic solvent) 33 parts V65 (polymerization initiator) 0.1 part

  After replacing the air in the polymerization tank with nitrogen gas, the reaction was started by heating to 60 ° C. with stirring in a nitrogen atmosphere. A mixture of the α, β-ethylenically unsaturated compound, the polymerization initiator, and the organic solvent was dropped from the dropping device over about 2 hours at the reflux temperature. After completion of the dropwise addition, the mixture was further aged with stirring for 6 hours, and then 160 parts of ethyl acetate was added and cooled to room temperature to obtain a copolymer (A) solution having a nonvolatile concentration of about 30%. This solution is colorless and transparent, has a non-volatile concentration of 30.5% by weight, a solution viscosity of 6,000 mPa · s (23 ° C.), and the copolymer (A) has a glass transition temperature of −36 ° C., a hydroxyl value of 9 mgKOH. / G, and the weight average molecular weight was 1,300,000.

<Synthesis Examples 2-18>
Compound (a2-2) is charged to the polymerization tank in the materials listed in Table 1, and compound (a1), compound (a2-1), organic solvent and polymerization initiator are charged in half to the polymerization tank and the dropping device. Except for the above, copolymer solutions were synthesized in the same manner as in Synthesis Example 1, respectively. The solution appearance, non-volatile content concentration (NV), solution viscosity (Vis), weight average molecular weight (Mw), hydroxyl value (OHV) and glass transition temperature (Tg) of the obtained copolymer were determined according to the following methods, and the results were obtained. Are shown in Table 1.

<< Solution appearance >>
The solution appearance of the copolymer obtained in each synthesis example was observed and evaluated visually.

<Measurement of nonvolatile content concentration (NV)>
About 1 g of the copolymer solution obtained in each synthesis example was weighed into a metal container, dried in an oven at 150 ° C. for 20 minutes, the residue was weighed, and the remaining rate was calculated, and the non-volatile concentration ( Solid unit) (unit:%).

<< Solution viscosity (Vis) >>
About 1.2 ml of the copolymer solution obtained in each synthesis example was measured with an E-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) in an atmosphere at 23 ° C., and the rotational speed was 0.5. Measured under a condition of ˜100 rpm for 1 minute, and set as a solution viscosity (mPa · s).

《Average molecular weight》
For the measurement of the number average molecular weight (Mn) and the weight average molecular weight (Mw), GPC (gel permeation chromatography) manufactured by Showa Denko KK was used. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined in terms of polystyrene as a standard substance.
Device name: Showa Denko GPC (Gel Permeation Chromatography) “Shodex GPC System-21”
Column: Tosoh GMHXL 4 and Tosoh HXL-H 1 were connected in series.
Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Column temperature: 40 ° C

<< Hydroxyl value (OHV) >>
About 1 g of a sample was accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. Next, 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for 1 hour. To this, phenolphthalein test solution was added as an indicator and held for 30 seconds. Thereafter, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The hydroxyl value was determined by the following formula. The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Non-volatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

<< Glass transition temperature (Tg) >>
An “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) and used for measurement. About 10 mg of a sample is put in an aluminum pan, weighed and set in a differential scanning calorimeter, and kept for 5 minutes at a temperature of 100 ° C. using the same type of aluminum pan without a sample as a reference. It was rapidly cooled to 120 ° C. Thereafter, the glass transition temperature (Tg, unit: ° C.) was determined from the DSC chart obtained by raising the temperature at a heating rate of 10 ° C./min.

The materials used in the synthesis examples are shown below. In Table 1, a blank means no blending.
Compound (a1-1)
2HEA: 2-hydroxyethyl acrylate, 4HBA: 4-hydroxybutyl acrylate compound (a1-2)
HPPA: 2-hydroxy-3-phenoxypropyl acrylate / compound (a2-1)
BA: n-butyl acrylate, 2EHA: 2-ethylhexyl acrylate, LMA: lauryl methacrylate / compound (a2-2)
MA: methyl acrylate, MMA: methyl methacrylate, PHEA: phenoxyethyl acrylate, AA: acrylic acid / polymerization initiator V65: 2,2′-azobis (2,4-dimethylvaleronitrile) [Wako Pure Chemical Industries, Ltd. “V65”], PBO: t-butyl peroxy-2-ethylhexanoate [“Perbutyl O” manufactured by NOF Corporation]
Organic solvent Ace: acetone, MEK: methyl ethyl ketone, MeAc: methyl acetate, EAc: ethyl acetate In the column of organic solvent in Table 1, the notation “Ace / EAc” is “organic solvent during copolymer polymerization” / Dilution solvent "means that the organic solvent at the time of copolymer polymerization used Ace, and the dilution solvent used EAc.

Using the copolymers obtained in the synthesis examples shown in Table 1, pressure-sensitive adhesives were prepared by the following methods.
(Examples 1-90, Comparative Examples 1-14)
For 100 parts of the copolymer (A) obtained in each synthesis example, a compound having one or more P-OH or a compound (B) capable of forming one or more P-OH by hydrolysis, an amino group or The silane compound (C) having an epoxy group and the polyisocyanate compound (D) are essential components. If necessary, the silane compound (E), the epoxy compound (F), and other components (Q) are added as shown in Table 2. The pressure-sensitive adhesive was obtained by adding the additional solvent such as ethyl acetate and adjusting the non-volatile content concentration to about 30%. The obtained pressure-sensitive adhesive was applied to each substrate, dried, and bonded, and the pressure-sensitive adhesive film was evaluated by the following method. The results are shown in Table 2.

<< Evaluation of pot life >>
About the pressure-sensitive adhesive obtained above, after blending, the viscosity at 25 ° C. is changed every 8 hours until 8 hours later using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 25 ° C., 12 rpm, 1 minute rotation Measurement was performed under the conditions, and pot life (pot life) was evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: Viscosity increase rate up to 8 hours is less than 1.2 times. Good.
Δ: Viscosity increase rate up to 8 hours is 1.2 times to less than 2 times. Practically usable x: Turbidity occurs in less than 8 hours, gelation occurs, or viscosity increase rate is 2 times or more. Not practical.

<Evaluation of coatability>
The pressure-sensitive adhesive is dried on a polyethylene terephthalate film (Therapy MF: manufactured by Toray Film Processing Co., Ltd., hereinafter referred to as “release liner”) having a thickness of 38 μm as a base material to a thickness of 25 μm after drying. The adhesive layer was formed by drying with hot air at 100 ° C. for 2 minutes. Next, a 100 μm thick polyethylene terephthalate film (polyester film) was bonded to the coated surface to produce a pressure-sensitive adhesive film. And the adhesive layer surface (coating surface) after peeling a peeling liner was observed visually, and it evaluated in three steps. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: A smooth coated surface was obtained. Good.
Δ: Slight repellency and foaming are observed at the end of the coated surface, but can be used practically.
X: Repelling, foaming and streaking are recognized on the coated surface, which is defective.

<Measurement of peel strength>
The pressure-sensitive adhesive film was cut to a width of 25 mm, the release liner was peeled off, and the exposed adhesive layer was attached to a non-alkali glass plate having a thickness of 100 μm using a laminator in an environment of 23 ° C. and a relative humidity of 50%. . Then, it hold | maintained for 20 minutes in the autoclave of conditions of 50 degreeC and 5 atmospheres, and obtained the measurement sample. The measurement sample was allowed to stand at 23 ° C. for 1 day, and was then peeled at a peeling speed of 300 mm / min and a peeling angle using a tensile tester (“Tensilon” manufactured by Orientec Co., Ltd.) in an environment of 23 ° C. and 50% relative humidity. The peel strength was measured under the condition of 180 degrees (measurement of peel strength one day after bonding). Moreover, after leaving the said measurement sample to stand at 23 degreeC for 14 days, peeling strength was measured by the same method (peeling strength measurement after 14 days of bonding). This peel strength was evaluated as an adhesive strength in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: Peel strength is 8.0 (N / 25 mm) or more and less than 12.0 (N / 25 mm). Good.
Δ: Peel strength is 5.0 (N / 25 mm) or more and less than 8.0 (N / 25 mm), or peel strength is 12.0 (N / 25 mm) or more and less than 15.0 (N / 25 mm). Can be used practically.
X: Peel strength is less than 5.0 (N / 25 mm), or 15.0 (N / 25 mm) or more. Bad.

<< Evaluation of optical characteristics >>
The pressure-sensitive adhesive was applied on the release liner so that the thickness after drying was 25 μm, and dried with hot air at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. Next, a separately prepared release liner was bonded to the adhesive layer to prepare a sample in which the adhesive layer was sandwiched between the release liners.
Next, both release liners were removed, the appearance of the pressure-sensitive adhesive layer alone was visually determined, and HAZE was measured by “NDH-300A (Nippon Denshoku Industries Co., Ltd.)”. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No cloudiness or the like is observed, and HAZE: less than 0.5. Good.
Δ: No cloudiness or the like is observed, but HAZE: 0.5 or more and less than 2, and can be used without any practical problem.
X: Cloudiness is observed or HAZE: 2 or more. Bad.

<< Evaluation of workability >>
The pressure-sensitive adhesive film was cut into a width of 100 mm and a length of 100 mm, 30 sheets of this were stacked, and the adhesive layer protruded from the edge of the adhesive film when pressed at 40 ° C.-60 Kg / cm ² for 1 hour. The state was evaluated in three stages as follows. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No protruding adhesive layer is observed. Good.
Δ: Protrusion of the adhesive layer of less than 0.3 mm is observed, but can be used practically.
X: Protrusion of the adhesive layer of 0.3 mm or more is observed. Bad.

<Evaluation of foaming peeling resistance>
The pressure-sensitive adhesive film is cut into a width of 100 mm and a length of 100 mm, the release liner is peeled off, and bonded and fixed to a polycarbonate (PC) plate, and a pressure of 0.5 MPa is applied at 50 ° C. for 20 minutes. A test piece (optical laminate) having a layer structure of “polyester film / pressure-sensitive adhesive layer / PC plate” held in an autoclave was produced. Using the test piece, a heat treatment (heat resistance test) was performed in an oven at 80 ° C. for 24 hours. After this heat resistance test, the adhesion interface (the interface between the pressure-sensitive adhesive layer and the PC plate) of the test piece was visually observed and evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No bubbles or floats are observed, and it is good.
Δ: Fine bubbles and floats are slightly observed at the end, but can be used practically.
X: Bubbles and floats were observed over the entire surface. Bad.

<Evaluation of light leakage>
The pressure-sensitive adhesive was dried on a 38 μm-thick polyethylene terephthalate film (Therapy MF: manufactured by Toray Film Processing Co., Ltd.) (hereinafter referred to as “release liner”) as a base material. Was applied to a thickness of 25 μm and dried with hot air at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. Next, both surfaces of a polyvinyl alcohol (PVA) polarizing film (HLC2-5618: manufactured by SANRITZ) are sandwiched between the adhesive layers as an optical film (I) with a triacetyl cellulose film (hereinafter referred to as “TAC film”). One side of a polarizing film with a laminated structure is bonded, and then aged for one week under conditions of a temperature of 35 ° C. and a relative humidity of 55%, and an optical structure having a configuration of “release liner / pressure-sensitive adhesive layer / TAC film / PVA / TAC film” A pressure-sensitive adhesive film (also referred to as a polarizing film adhesive sheet) was obtained.
It cut | judged to 80 mm x 150 mm so that the axial direction of the absorption axis of said polarizing film adhesive sheet may become an angle of 45 degrees with respect to a long side. Next, the release liner is peeled off, and the exposed pressure-sensitive adhesive layer is arranged on both surfaces of a non-alkali glass plate having a thickness of 0.4 mm so that the axial directions of the respective absorption axes are orthogonal to each other in a 50 ° C. atmosphere. After applying pressure of 5 kg / cm ² and holding it in an autoclave for 20 minutes, leaving it in an atmosphere of 80 ° C. for 500 hours, returning it to room temperature, and checking for light leakage from the four corners or peripheral edges It observed visually and evaluated in three steps as light leakage. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No light leakage is observed. Good.
Δ: Light leakage is slightly noticeable, but can be used practically.
X: Light leakage is very remarkable. Bad.

<< Evaluation of removability (reworkability) >>
The polarizing film adhesive sheet is cut into a size of 25 mm × 150 mm, the release liner is peeled off, and is attached to a float glass plate with a thickness of 1.1 mm using a laminator, and placed in an autoclave at 50 ° C. and 5 atm. It was held for 20 minutes to obtain an optical laminate of a polarizing film adhesive sheet and a glass plate.
The polarizing film of this laminated body was peeled off at a speed of 300 mm / min in the direction of 180 °, and the fogging of the glass surface after peeling was visually observed and evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No cloudiness and no problem in practical use. Very good.
Δ: Some cloudiness is observed, but there is no practical problem. Good.
X: Transfer of the pressure-sensitive adhesive is recognized over the entire surface, and is not practical.

<< Evaluation of durability (heat resistance, heat and humidity resistance) >>
The release liner of the polarizing film adhesive sheet is peeled off, and the exposed pressure-sensitive adhesive layer is subjected to a pressure of 5 kg / cm ² in a 50 ° C. atmosphere on one side of a non-alkali glass plate having a thickness of 0.4 mm and autoclaved for 20 minutes. After being held and bonded together, it was left in an atmosphere at 80 ° C. for 500 hours (heat resistance test). Similarly, the sample was left in a constant temperature and humidity chamber at 60 ° C. and 90% relative humidity for 500 hours (moisture and heat resistance test).
After standing, the temperature was returned to room temperature, and the state of the polarizing film adhesive sheet floating / peeling, foaming and cracking was visually observed and evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
Foaming is a state in which relatively large bubbles are generated at the interface (other than the peripheral edge) between the pressure-sensitive adhesive layer and the glass.
The floating / peeling is a state where the polarizing film adhesive sheet is lifted from the glass and peeled off.
The crack is a state in which fine bubbles having a diameter of 1 mm or less are generated in a streak-like manner at the peripheral edge of the polarizing film adhesive sheet.
Each evaluation standard is as follows.
○: No foaming, floating / peeling or cracking occurs. Good.
Δ: Minor occurrence of foaming, floating, peeling or cracking of 0.5 mm or less is observed, but it can be used practically.
X: Remarkable generation | occurrence | production, such as foaming, a float, peeling, a crack, is recognized over the whole surface. Cannot be used practically.

The materials used in the examples are shown below. In Table 2, a blank means no blending.
・ Copolymer (A)
Synthesis example: Copolymer / compound (B) obtained in each synthesis example shown in Table 1
OPA: orthophosphoric acid, PPA: polyphosphoric acid, MPK: potassium metaphosphate, PTA: triethanolamine phosphate, PTE: triethyl phosphate compound (C)
MAS: 3-aminopropyltrimethoxysilane, DAS: N- (2-aminomethyl) 3-aminopropyltrimethoxysilane, EPS: 3-glycidoxypropyltrimethoxysilane, CHS: 2- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane-compound (D)
TDI / TMP: trimethylolpropane adduct of tolylene diisocyanate, XDI / TMP: trimethylolpropane adduct of xylylene diisocyanate / compound (E)
HTS: Hexyltrimethoxysilane compound (F)
TGXA: N, N, N ′, N′-tetraglycidyl-m-xylylenediamine component (Q)
AO50: Phenolic antioxidant “ADK STAB AO-50 (manufactured by Adeka)”
Additional solvent EAc: ethyl acetate

  As described above, in Examples 1, 2, 19 to 27, 34, and 46 to 90, the pressure-sensitive adhesive of the present invention is solution aging stability, coatability, peel strength, optical properties, workability, It can be seen that the foam exfoliation property, light leakage property, rework property, heat resistance, and wet heat resistance are all excellent. Further, in Examples 3 to 18, 28 to 33, and 35 to 45, although there are portions where the level of each evaluation is low, it has become clear that they can be used without any practical problem. On the other hand, in Comparative Examples 1 to 14, any of pot life, coatability, peel strength, optical properties, workability, foam peeling resistance, light leakage property, rework property, heat resistance, and wet heat resistance It became clear that it was extremely inferior and had practical problems.

  Since the pressure-sensitive adhesive according to the present invention has excellent adhesive strength, it can be used in the construction field (eg, exterior, interior, equipment, etc.), electrical equipment field (eg, home appliances, kitchen equipment, air conditioning, etc.), and transport equipment field. It can also be used in various industrial fields other than the optical field, such as the ship field, automobiles, etc., the furniture field, and the sundries field.

Claims (8)

  An α, β-unsaturated double bond group-containing compound (a1) having one or more hydroxyl groups in the molecule and an α, β-unsaturated double bond group-containing compound (a2) having no hydroxyl groups in the molecule A copolymer (A) obtained by polymerizing a monomer mixture and having a weight average molecular weight of 100,000 to 2,000,000 and a hydroxyl value of 0.1 to 50 mgKOH / g, and at least one P-OH A pressure-sensitive adhesive containing a compound or a compound (B) capable of forming one or more P-OH by hydrolysis, a silane compound (C) having an amino group or an epoxy group, and a polyisocyanate compound (D).   0.01 to 10 parts by weight of a compound having one or more P—OH or a compound (B) capable of forming one or more P—OH by hydrolysis with respect to 100 parts by weight of the copolymer (A) The pressure-sensitive adhesive according to claim 1, comprising 0.01 to 10 parts by weight of a silane compound (C) having a group or an epoxy group and 0.1 to 30 parts by weight of a polyisocyanate compound (D). Agent.   The pressure-sensitive type according to claim 1 or 2, wherein the compound having one or more P-OH or the compound (B) capable of forming one or more P-OH by hydrolysis is phosphoric acid (b1). adhesive.   Furthermore, the silane compound (E) which does not have an amino group and an epoxy group is contained, The pressure sensitive adhesive in any one of Claims 1-3 characterized by the above-mentioned.   A pressure-sensitive adhesive film obtained by laminating an adhesive layer containing the pressure-sensitive adhesive according to any one of claims 1 to 4 on at least one surface of a substrate (G).   The pressure-sensitive adhesive film according to claim 5, wherein the substrate (G) is a transparent film (H).   The pressure-sensitive adhesive film according to claim 6, wherein the transparent film (H) is an optical film (I).   An optical laminate comprising an optical film (I), an adhesive layer formed from the pressure-sensitive adhesive according to any one of claims 1 to 4, and glass.